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WO2007136012A1 - Liquide de revêtement destiné à former une couche sous-jacente dans un photorécepteur électrophotographique et procédé de fabrication de ce liquide - Google Patents

Liquide de revêtement destiné à former une couche sous-jacente dans un photorécepteur électrophotographique et procédé de fabrication de ce liquide Download PDF

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Publication number
WO2007136012A1
WO2007136012A1 PCT/JP2007/060272 JP2007060272W WO2007136012A1 WO 2007136012 A1 WO2007136012 A1 WO 2007136012A1 JP 2007060272 W JP2007060272 W JP 2007060272W WO 2007136012 A1 WO2007136012 A1 WO 2007136012A1
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WO
WIPO (PCT)
Prior art keywords
undercoat layer
photosensitive member
electrophotographic photosensitive
coating solution
oxide particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2007/060272
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English (en)
Japanese (ja)
Inventor
Teruyuki Mitsumori
Kozo Ishio
Hiroe Fuchigami
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to CN2007800155250A priority Critical patent/CN101432662B/zh
Publication of WO2007136012A1 publication Critical patent/WO2007136012A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/142—Inert intermediate layers
    • G03G5/144—Inert intermediate layers comprising inorganic material

Definitions

  • the present invention relates to a coating solution for forming an undercoat layer for an electrophotographic photosensitive member, a method for producing a coating solution for forming an undercoat layer used when forming and drying an undercoat layer of an electrophotographic photosensitive member,
  • the present invention relates to a photosensitive member having a photosensitive layer on an undercoat layer formed by applying a coating solution by the method, an image forming apparatus using the photosensitive member, and an electrophotographic cartridge using the photosensitive member.
  • An electrophotographic photosensitive member having a photosensitive layer on an undercoat layer formed by applying and drying the coating solution for forming an undercoat layer of the present invention is suitably used for electrophotographic printers, facsimiles, copiers and the like. be able to.
  • an organic photoreceptor is formed by forming a photosensitive layer on a conductive support, but it has a single-layer photosensitive layer in which a photoconductive material is dissolved or dispersed in a binder resin.
  • V so-called multi-layer photoreceptors, etc. having a photosensitive layer composed of a plurality of layers in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated are known. Speak.
  • Layers of organophotoreceptors are usually dissolved in various solvents due to their high productivity. Alternatively, it is formed by coating and drying the dispersed coating solution.
  • the coating solution for forming the undercoat layer is formed by coating with a coating solution in which metal oxide particles are dispersed.
  • Such a coating liquid is obtained by wet-dispersing titanium oxide particles in an organic solvent with a known mechanical grinding device such as a ball mill, a sand grind mill, a planetary mill, or a roll mill for a long time. It was common to manufacture (for example, refer patent document 1).
  • a known mechanical grinding device such as a ball mill, a sand grind mill, a planetary mill, or a roll mill for a long time.
  • a known mechanical grinding device such as a ball mill, a sand grind mill, a planetary mill, or a roll mill for a long time.
  • a known mechanical grinding device such as a ball mill, a sand grind mill, a planetary mill, or a roll mill for a long time.
  • the metal oxide particles in the coating liquid for forming the undercoat layer are dispersed using a dispersion medium, the material of the dispersion medium is changed to a titer or zircoyu, so that charging is possible even under
  • Patent Document 1 JP-A-11 202519
  • Patent Document 2 JP-A-6-273962
  • the present invention has been made in view of the background of the above-described electrophotographic technology, and has a coating solution for forming an undercoat layer having high stability, and forms an image with high image quality even under various use environments.
  • Image defects such as black spots, color spots, capri, and the like, and high-performance electrophotographic photoconductors, image forming apparatuses using the photoconductors, and electrophotographic power using the photoconductors
  • the objective is to provide a cartridge.
  • the inventors of the present invention have developed a coating solution for forming an undercoat layer with high performance by controlling the particle size of the metal oxide particles in the coating solution for forming the undercoat layer within a specific range.
  • a dispersion medium used for dispersion at that time it is possible to use a dispersion medium having a smaller particle diameter than that of a dispersion medium that is usually used. It was found that a coating solution for forming an undercoat layer having excellent stability can be obtained, and the present invention has been achieved.
  • an electrophotographic photosensitive member having an undercoat layer obtained by applying and drying the coating solution has good electrical characteristics even in different usage environments, and according to an image forming apparatus using the photosensitive member. It is possible to form high-quality images, and image defects such as black spots and color spots that are thought to occur due to dielectric breakdown are extremely difficult to see! However, it came to the present invention o
  • the present invention relates to a coating solution for forming an undercoat layer of an electrophotographic photosensitive member containing metal oxide particles and a curable binder resin, and the dynamics of metal oxide particles in the coating solution.
  • a coating solution for forming an undercoat layer of an electrophotographic photosensitive member characterized by having a volume average particle diameter Mv measured by a light scattering method of 0.1 ⁇ m or less (hereinafter abbreviated as “Aspect 1”) Is provided.
  • the present invention provides a coating solution for forming an undercoat layer of an electrophotographic photoreceptor containing metal oxide particles and a curable binder resin, and the dynamics of metal oxide particles in the coating solution.
  • the volume average particle diameter Mv measured by the light scattering method is 0.1 m or less, and the ratio MvZMp between the volume average particle diameter Mv and the number average particle diameter Mp satisfies the following formula (1).
  • a coating liquid for forming an undercoat layer of an electrophotographic photosensitive member (hereinafter abbreviated as “Aspect 2”) is provided.
  • Equation (1) 10 ⁇ Mv / Mp ⁇ 1. 40
  • the present invention also provides an average particle as the metal oxide particles in the method for producing a coating liquid for forming an undercoat layer of an electrophotographic photoreceptor containing metal oxide particles and a curable binder resin.
  • a method for producing a coating solution for forming an undercoat layer of an electrophotographic photosensitive member using metal oxide particles dispersed using a dispersion medium having a diameter of 5 ⁇ m to 200 ⁇ m hereinafter referred to as “Aspect 3”).
  • the present invention also provides an electrophotographic photoreceptor having an undercoat layer formed by coating and forming the above coating solution.
  • the present invention also provides an electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, and an image exposing unit that performs image exposure on the charged electrophotographic photosensitive member to form an electrostatic latent image.
  • An image forming apparatus having a developing means for developing the electrostatic latent image with toner and a transferring means for transferring the toner to a transfer target, wherein the electrophotographic photosensitive member is the above-described electrophotographic photosensitive member.
  • An image forming apparatus is provided.
  • the present invention also includes at least an electrophotographic photosensitive member, a charging unit that charges the electrophotographic photosensitive member, and a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member with toner.
  • An electrophotographic cartridge is provided, wherein the electrophotographic photosensitive member is the above-described electrophotographic photosensitive member.
  • the coating solution for forming the undercoat layer is in a stable state and can be stored and used for a long time without gelation or precipitation of the dispersed metal oxide particles. It becomes.
  • the coating solution when used, changes in physical properties such as viscosity are reduced, and when the coating layer is continuously coated on the support and dried to form the coating layer, The film thickness becomes uniform.
  • an electrophotographic photoreceptor having an undercoat layer formed using the coating liquid of the present invention has stable electrical characteristics even at low temperatures and low humidity, and is excellent in electrical characteristics. According to the image forming apparatus using the electrophotographic photosensitive member of the present invention, it is possible to form an excellent image with extremely few image defects such as black spots and color spots, and particularly to the electrophotographic photosensitive member. In the image forming apparatus charged by the charging means arranged in contact, a good image with extremely few image defects such as black spots and color spots can be formed. In particular, an electrophotographic photosensitive member having an undercoat layer formed using the coating liquid of the present invention is used, and the wavelength of light used for image exposure means is 350 ⁇ ! According to the image forming apparatus of ⁇ 600 nm, a high quality image can be obtained because the initial charging potential and sensitivity are high.
  • FIG. 1 is a longitudinal sectional view of a wet stirring ball mill according to the present invention.
  • FIG. 2 is a powder X-ray diffraction spectrum pattern with respect to CuK ⁇ characteristic X-ray of oxytitanium phthalocyanine used as a charge generation material in Examples.
  • FIG. 3 is a schematic view showing a main configuration of an embodiment of an image forming apparatus provided with the electrophotographic photosensitive member of the present invention.
  • FIG. 4 is an enlarged longitudinal sectional view of a main part of a mechanical seal used in a wet stirring ball mill according to an embodiment of the present invention.
  • FIG. 5 is a longitudinal sectional view of another example of a wet stirring ball mill according to an embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of the separator of the wet stirring ball mill shown in FIG.
  • the present invention relates to a coating solution for forming an undercoat layer of an electrophotographic photosensitive member (hereinafter sometimes simply referred to as "coating solution”), a method for producing a coating solution, and coating and forming the coating solution.
  • coating solution for forming an undercoat layer of an electrophotographic photosensitive member
  • the present invention relates to an electrophotographic photosensitive member having an undercoat layer, an image forming apparatus using the electrophotographic photosensitive member, and an electrophotographic cartridge using the electrophotographic photosensitive member.
  • the electrophotographic photoreceptor of the present invention has an undercoat layer and a photosensitive layer on a conductive support.
  • the undercoat layer according to the present invention is provided between the conductive support and the photosensitive layer, improves the adhesiveness between the conductive support and the photosensitive layer, conceals dirt or scratches on the conductive support, and does not Prevention of carrier injection due to inhomogeneity of pure materials and surface properties, improvement of non-uniformity of electrical characteristics, prevention of surface potential decrease due to repeated use, prevention of local surface potential fluctuations that cause image quality defects, etc.
  • This layer has at least one of the above functions and is not essential for the development of photoelectric characteristics.
  • the undercoat layer-forming coating solution that is Embodiment 1 of the present invention is used to form an undercoat layer of an electrophotographic photoreceptor, and dynamic light scattering of metal oxide particles contained in the coating solution.
  • Volume average particle diameter measured by the method Mv force is 0.1 m or less.
  • the metal oxide particles in the coating solution for forming the undercoat layer of the electrophotographic photoreceptor of the present invention are preferably present as primary particles, but in most cases, aggregate secondary particles are mixed. Therefore, it is very important how the particle size distribution should be in that state. According to the definition below, both primary particles and aggregate secondary particles are measured.
  • the “volume average particle diameter Mv” of the metal oxide particles contained in the coating solution for forming the undercoat layer is a cumulative curve with the total volume of the metal oxide particles being 100%.
  • the cumulative curve is defined as the particle size at which the small particle size side force is counted to 50% by volume.
  • the "cumulative 90% particle size" of the metal oxide particles contained in the coating solution for forming the undercoat layer described below is a cumulative curve with the total volume of the metal oxide particles being 100%.
  • the product curve is defined as the particle size at which the volume is 90% counted from the small particle size side.
  • volume average particle diameter Mv and “cumulative 90% particle diameter” are both measured by a dynamic light scattering method.
  • the dynamic light scattering method the speed of Brownian motion of finely dispersed particles is detected, and the particle size is determined by irradiating the particles with laser light and detecting light scattering (Doppler shift) with different phases according to the speed. The distribution is obtained.
  • the values of “volume average particle size ⁇ ”, “number average particle size ⁇ ”, and “cumulative 90% particle size” of the metal oxide particles in the coating solution of the present invention are as follows. This is the value when the oxide particles are stably dispersed, and means the particle size of the metal oxide particles as the powder before dispersion and the metal oxide particles in the wet cake. ! /
  • volume average particle size ⁇ and “cumulative 90% particle size” are both dynamic light scattering particle size analyzers (MICROTRAC UPA model: 9340-UPA, manufactured by Nikkiso Co., Ltd.) (hereinafter "UPA” Is abbreviated to be measured with the following settings.
  • UPA dynamic light scattering particle size analyzers
  • the specific measurement operation shall be performed based on the instruction manual for the above particle size analyzer (manufactured by Nikkiso Co., Ltd., Document No. T15-490A00, Revision No. E).
  • NZA Particle refractive index
  • Dispersion medium refractive index 1.35
  • the volume average particle diameter Mv of the metal oxide particles contained in the coating liquid of embodiment 1 of the present invention measured by the dynamic light scattering method is essential to be 0.1 m or less.
  • the force is preferably 0.095 ⁇ m or less, more preferably 0.090 ⁇ m or less. Further, it is usually 0.02 ⁇ m or more, preferably 0.04 ⁇ m or more.
  • the 90% cumulative particle size of the metal oxide particles contained in the coating liquid of aspect 1 of the present invention is not particularly limited, but is preferably 0.3 m or less. It is preferably 25 ⁇ m or less, more preferably 0.25 m or less. Further, it is usually 0.02 / z m or more, preferably 0.04 ⁇ m or more.
  • the coating solution is in a stable state, and does not gel or precipitate the dispersed metal oxide particles.
  • changes in physical properties such as the viscosity of the coating liquid are reduced, and the film thickness becomes uniform when continuously coated on a support and dried to form an undercoat layer.
  • an electrophotographic photoreceptor having an undercoat layer formed using a coating solution having a powerful particle size has stable electrical characteristics even at low temperatures and low humidity, and is excellent in electrical characteristics.
  • the coating solution for forming the undercoat layer according to aspect 2 of the present invention is used to form an undercoat layer of the electrophotographic photosensitive member, and the metal oxide particles contained in the coating solution contain dynamic light scattering.
  • the volume average particle diameter Mv measured by the method is 0.1 ⁇ m or less, and the ratio “MvZMp” of the volume average particle diameter Mv to the number average particle diameter Mp satisfies the following formula (1) It is.
  • Equation (1) 10 ⁇ Mv / Mp ⁇ 1. 40
  • the metal oxide particles in the coating solution for forming the undercoat layer of the electrophotographic photosensitive member of the present invention should be present as primary particles, usually such a case is rare and aggregation occurs. In most cases, they are present as aggregate secondary particles or a mixture of both. Therefore, how the particle size distribution should be in that state is very important. According to the definition below, both primary particles and aggregate secondary particles are measured.
  • the volume average particle diameter Mv of the metal oxide particles in the coating liquid By setting the thickness to 0.1 ⁇ m or less, the film thickness and surface properties after forming the undercoat layer become uniform as a result of less precipitation and viscosity change in the liquid. On the other hand, when the volume average particle diameter Mv of the metal oxide particles exceeds 0.1 ⁇ m, conversely, precipitation and viscosity change in the liquid are large, resulting in the film thickness and surface properties after forming the subbing layer. This may cause adverse effects on the quality of the upper layers (such as charge generation layers).
  • the volume average particle diameter Mv of the metal oxide particles in the coating solution is preferably 0.095 ⁇ m or less, more preferably 0.090 ⁇ m or less. Further, it is usually 0.02 ⁇ m or more, preferably 0.04 ⁇ m or more.
  • Equation (2) 20 ⁇ MvZMp ⁇ 1. 35
  • the volume average particle diameter Mv and the number average particle diameter Mp of the metal oxide particles are whatever the form of the metal oxide particles in the coating solution for forming the undercoat layer. This is a value obtained by directly measuring the particle diameter of the object particles by the dynamic light scattering method.
  • the dynamic light scattering method detects the speed of Brownian motion of finely dispersed particles, and irradiates the particles with a single laser beam to detect light scattering (Doppler shift) with different phases according to the speed.
  • Doppler shift light scattering
  • the value of the particle diameter of the metal oxide particles in the coating liquid of aspect 2 of the present invention is a value when the metal oxide particles are stably dispersed in the coating liquid system, and is before dispersion. This means the particle diameter of the metal oxide particles as the powder, and the particle diameter of the metal oxide particles in the wet cake.
  • the "volume average particle diameter Mv” and the “number average particle diameter Mp" are defined as those measured using the above UPA with the following settings.
  • For specific measurement operation please refer to the manual for the above particle size analyzer (manufactured by Nikkiso Co., Ltd., Document No. T15-490A00, revised
  • NZA Particle refractive index
  • Dispersion medium refractive index 1.35
  • the "volume average particle diameter Mv” and the “number average particle diameter Mp” are the following formulas (A), from the results of the particle size distribution of the particles obtained by the above measurement, respectively: This is the value obtained by calculation using equation (B).
  • n represents the number of particles
  • V represents the volume of the particles
  • d represents the particle diameter.
  • a coating solution that satisfies the requirements of both Embodiment 1 and Embodiment 2 of the present invention is further in a stable state, causing gelation and precipitation of dispersed metal oxide particles. There is no. Furthermore, changes in physical properties such as the viscosity of the coating solution are reduced, and the film thickness is uniform.
  • an electrophotographic photosensitive member having an undercoat layer formed using a coating solution having a strong particle size has stable electric characteristics even at low temperature and low humidity and is excellent in electric characteristics.
  • metal oxide particles according to the present invention any metal oxide particles that can be generally used for an electrophotographic photoreceptor can be used. More specifically, metal oxide particles containing one kind of metal element such as titanium oxide, acid aluminum, silicon oxide, acid zirconium, zinc oxide, iron oxide, etc. And metal oxide particles containing a plurality of metal elements such as calcium titanate, strontium titanate, and barium titanate. Among these, metal oxide particles having a band gap of 2 eV to 4 eV are preferable. As the metal oxide particles, only one type of particles may be used, or a plurality of types of particles may be mixed and used.
  • metal oxide particles containing one kind of metal element such as titanium oxide, acid aluminum, silicon oxide, acid zirconium, zinc oxide, iron oxide, etc.
  • metal oxide particles containing a plurality of metal elements such as calcium titanate, strontium titanate, and barium titanate.
  • metal oxide particles having a band gap of 2 eV to 4 eV are preferable.
  • the metal oxide particles
  • titanium oxide particles aluminum oxide particles, silicon oxide particles or acid-zinc particles are preferable, more preferably acid-titanium particles or acid-aluminum particles.
  • Oxidized titanium particles are particularly preferred. Any of rutile, anatase, brookite, and amorphous can be used as the crystalline form of the titanium oxide particles. In addition, those having different crystal states may be included in a plurality of crystal states.
  • the surface of the metal oxide particles may be subjected to various surface treatments. For example, treatment with inorganic substances such as acid tin, acid aluminum, antimony oxide, acid zirconium, and silicon oxide, or organic substances such as stearic acid, polyol, and organosilicon compound may be performed. In particular, in the case of using titanium oxide particles, it is preferable that the surface is treated with an organosilicon compound.
  • inorganic substances such as acid tin, acid aluminum, antimony oxide, acid zirconium, and silicon oxide
  • organic substances such as stearic acid, polyol, and organosilicon compound
  • organosilicon compounds include silicone oils such as dimethylpolysiloxane and methylhydrogenpolysiloxane; methyldimethoxysilane; organosilanes such as diphenyldimethoxysilane; silazanes such as hexamethyldisilazane; Silane treatment agents represented by the structure of the following general formula (1), which are preferred for silane coupling agents such as orchid, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and the like, are metal oxide particles. Is the best treatment agent.
  • R 1 and R 2 each independently represent an alkyl group, and R 3 represents an alkyl group or an alkoxy group.
  • R 1 and R 2 each independently represents an alkyl group, preferably a methyl group or an ethyl group.
  • R 3 represents an alkyl group or an alkoxy group, preferably a methyl group, an ethyl group, a methoxy group or an ethoxy group.
  • the outermost surface of these surface-treated metal oxide particles is preferably treated with the treatment agent as described above, before the treatment, aluminum oxide, silicon oxide, zirconium oxide It is also preferable to be treated with a treating agent such as a comb.
  • titanium oxide particles only one type of particles including crystal type and surface treatment may be used, or a plurality of types of particles may be mixed and used.
  • the metal oxide particles to be used those having an average primary particle diameter of 500 nm or less are usually used, preferably those having a particle diameter of 1 nm to 100 nm, more preferably those having a particle diameter of 5 nm to 50 nm.
  • This “average primary particle size” is obtained by directly observing metal oxide particles with a transmission electron microscope (hereinafter sometimes abbreviated as “TEM”). It is defined as the arithmetic mean value of the particle diameter.
  • metal oxide particles to be used those having various refractive indexes can be used.
  • any metal oxide particles can be used as long as they can be used for an electrophotographic photoreceptor. Can also be used.
  • those having a refractive index of 1.4 or more and a refractive index of 3.0 or less are used.
  • the refractive index of metal oxide particles is described in various publications. For example, according to the filler application dictionary (edited by Filler Ikenkai, Taiseisha, 1994), as shown in Table 1 below. It has become.
  • the specific product name of the acid oxide titanium particles is “TTO-55 (N ) ", Al O coating
  • TTO-55 (S) an ultra-fine particulate titanium oxide surface-treated with nosiloxane, “CR—EL”, a high purity titanium oxide, and “R—550”, a sulfuric acid method titanium oxide.
  • TR-700 surface-treated with SiO, Al 2 O, ZnO, SiO, A
  • TR-840 “TA-500” surface-treated with 1 O
  • TA-100 “TA-200”, “T A-300 ”surface-treated untreated titanium oxide
  • TA-400 surface treatment with Al 2 O
  • MT-100SAS “MT-500SAS” (hereinafter referred to as surface treatment with 2 2 3 2 2 and organosiloxane)
  • Al oxide particles include "Aluminium Oxide C” (manufactured by Nippon Aerosil Co., Ltd.).
  • Specific product names of silicon oxide particles include “200CF”, “R972” (manufactured by Nippon Aerosil Co., Ltd.), “KEP-30” (manufactured by Nippon Shokubai Co., Ltd.), and the like.
  • Specific examples of the tin oxide particles include “SN-100P” (manufactured by Ishihara Sangyo Co., Ltd.).
  • a specific trade name for the acid zinc particles is “MZ-305SJ (manufactured by Tika).
  • the metal oxide particles usable in the present invention are limited to these. is not.
  • the metal oxide particles are in the range of 0.5 to 4 parts by weight with respect to 1 part by weight of the curable binder resin. It is preferable to use it. Particularly preferred is a range of 1 to 3 parts by weight.
  • the binder resin used in the coating solution for forming the undercoat layer of the electrophotographic photoreceptor according to the present invention is a curable binder resin.
  • the curable binder resin is soluble in an organic solvent, and the undercoat layer after formation is insoluble or low in solubility in an organic solvent used in a coating solution for forming a photosensitive layer. There is no particular limitation as long as it does not substantially dissolve.
  • One or more curable binder resins can be used in combination.
  • the undercoat layer may be dissolved or altered, and therefore, by using at least one curable binder resin, it is insoluble in the solvent or hardly soluble. You can make it.
  • the "curable binder resin” includes both cases where the resin itself has curability and cases where the curative is used in combination with a curing agent.
  • a mixture of fat and the curing agent is referred to as “curable binder resin”.
  • the "curable binder resin” that can be used for the undercoat layer is not particularly limited.
  • phenol resin, urea resin, melamine resin, urethane resin, unsaturated polyester resin, phenoxy resin examples include fats, epoxy greaves, polybulur pyrrolidone, polybulal alcohol, casein, poly (meth) acrylic acid, celluloses, gelatin, starch, polyimide, polyamide, etc., and if necessary, a mixture of these curing agents. .
  • the force-curable binder resin containing one or more kinds of curable binders includes a thermosetting resin, a photocurable resin, and an EB curable resin. Of these, thermosetting resin or photocurable resin is particularly preferable.
  • Thermosetting resin is a general term for types of resin that are cured by a chemical reaction caused by heat. Specific examples include phenol resin, urea resin, melamine resin, cured epoxy resin, urethane resin, and unsaturated polyester resin. Further, it is possible to impart curability by introducing a curable substituent into a normal thermoplastic polymer. In general, it is sometimes called a condensation-type cross-linking polymer, an addition-type cross-linking polymer, etc., and it is a polymer having a three-dimensionally crosslinked structure.
  • thermosetting binder resin is a synthetic resin made from phenol and formaldehyde and has the advantage that it can be easily and cleanly formed.
  • Phenolic resin is a synthetic resin made from phenol and formaldehyde and has the advantage that it can be easily and cleanly formed.
  • an acidic condition gives a molar ratio of FZP of about 0.6 to 1
  • a base catalyst produces a resin of about 1 to 3.
  • the urea resin is a synthetic resin obtained by reacting urea with formalin, and has an advantage that it can be freely colored with a colorless and transparent solid.
  • the reaction between urea and formaldehyde produces polymethylene urea having no methylol group under acidic conditions, and a mixture of methylol ureas is obtained under basic conditions.
  • Melamine rosin is a thermoset obtained by the reaction of a melamine derivative and formaldehyde. Although it is a curable resin and is more expensive than urea resin, it has the advantages of being excellent in hardness, water resistance, heat resistance, etc., having strength and being colorless and transparent and capable of being freely colored.
  • Epoxy resin is a general term for thermosetting resins that can be cured by graft polymerization with an epoxy group remaining in the polymer. This is called epoxy resin by mixing prepolymer and grafting agent before graft polymerization.
  • examples of the thermosetting binder resin in the present invention include epoxy resin in this state.
  • Prepolymers are mainly liquid compounds having two or more epoxy groups in one molecule.
  • a three-dimensional polymer is produced and becomes a cured epoxy resin.
  • the cured epoxy resin has good adhesion and adhesion, and is excellent in heat resistance, chemical resistance, and electrical stability.
  • General-purpose epoxy resins are those of bisphenol A diglycidyl ether, but also include glycidyl ester-based and glycidylamine-based resins and cycloaliphatic epoxy resins.
  • Typical examples of the curing agent are aliphatic or aromatic polyamines, acid anhydrides, and polyphenols, which react with an epoxy group by a heavy weight to polymerize and three-dimensionalize.
  • Others include tertiary amines and Lewis acids.
  • Urethane resin is a high molecular compound obtained by copolymerizing monomers with a urethane bond usually formed by condensation of an isocyanate group and an alcohol group. Usually, it is divided into a liquid main agent and a curing agent at room temperature, and the two liquids are cured by stirring and mixing.
  • the unsaturated polyester resin is separated into a liquid resin and a curing agent which are liquid at room temperature, and the two liquids are polymerized by stirring and mixing. Although it has a feature of high transparency, there is a problem with dimensional stability, etc., in which shrinkage during polymerization curing is large. Since it is often sold in the form of mixed volatile solvents, it may gradually deform as the solvent evaporates after curing.
  • the photocurable resin is a synthetic organic material that is cured by the action of light energy.
  • ultraviolet light is widely used as light for curing.
  • an ultraviolet laser is preferable because of its high energy density.
  • the photocurable resin is generally a composition composed of a monomer, an oligomer, a photopolymerization initiator, various additives, and the like.
  • the monomer is polymerized to become a large molecule, and plastic. It is an organic material that forms a hook.
  • An oligomer is a material in which a monomer is reacted in advance several times and is polymerized in the same way as a monomer to form a large molecule to form a plastic. Specific examples include epoxy acrylate and urethane acrylate.
  • a photopolymerization initiator for example, benzoin-based, acetophenone-based, etc.
  • the photopolymerization initiator absorbs light and becomes active (excited), causing reactions such as cleavage reaction, hydrogen abstraction, and electron transfer.
  • This reaction produces a substance that initiates a reaction such as radical molecules or hydrogen ions.
  • the generated radical molecules and hydrogen ions attack the oligomer and monomer molecules, causing a three-dimensional polymerization and cross-linking reaction.
  • the coating liquid for forming the undercoat layer of the present invention may further contain other resin.
  • other resin there is no particular limitation on the “other resin” that is strong, but polyamide resins such as alcohol-soluble copolymer polyamides and modified polyamides are preferred because they exhibit good dispersibility and coating properties.
  • polyamide resin examples include so-called copolymer nylon obtained by copolymerizing 6-nylon, 66-nylon, 610-nylon, 11-nylon, 12-nylon, N-alkoxymethyl-modified nylon, N —Alcohol-soluble nylon resin of the type obtained by chemically modifying nylon, such as alkoxyethyl-modified nylon.
  • Specific product names include, for example, “CM4000”, “CM8000” (above, manufactured by Torayen Earth), “F-30 K”, “MF-30”, “EF-30T” (above, manufactured by Nagase Chemtech). Is mentioned.
  • copolymer polyamide resins containing diamine represented by the following general formula (2) as a constituent component are particularly preferably used.
  • R 4 to R 7 each independently represents a hydrogen atom or an organic substituent.
  • m and n each independently represents an integer of 0 to 4, and when there are a plurality of substituents, these substituents may be different from each other.
  • a hydrocarbon group having 20 or less carbon atoms, which may contain a hetero atom is preferred, and a methyl group, an ethyl group, n Alkyl groups such as propyl group and isopropyl group; alkoxy groups such as methoxy group, ethoxy group, n-propoxy group and isopropoxy group; aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group; Can be mentioned. More preferred is an alkyl group or an alkoxy group, and particularly preferred is a methyl group or an ethyl group.
  • the copolymerized polyamide resin containing diamine represented by the general formula (2) as a constituent component is, for example, ratatas such as ⁇ -petit oral ratata, ⁇ -force prolatatam, lauryllatatam, etc .; 1 , 4 Butanedicarboxylic acid, 1,12 dodecanedicarboxylic acid, 1,20 dicarboxylic acids such as eicosanedicarboxylic acid; 1,4 butanediamine, 1,6 hexamethylenediamine, 1,8-otatamethylenediamine, 1,12 Dodecandiamine and other diamines; those obtained by combining piperazine and the like and copolymerized in binary, ternary, quaternary, etc.
  • ratatas such as ⁇ -petit oral ratata, ⁇ -force prolatatam, lauryllatatam, etc .
  • the copolymerization ratio is not particularly limited, but it is generally 5 mol% to 40 mol% with respect to all constituent components including diamine component dicarboxylic acid and ratatam represented by the general formula (2). Preferably, it is 5 mol% to 30 mol%.
  • the number average molecular weight of the copolymerized polyamide resin is preferably 10,000 to 50,000, and particularly preferably 15,000 to 35,000. If the number average molecular weight is too small or too large, it may be difficult to maintain film uniformity.
  • a normal polyamide polycondensation method without particular limitation is appropriately applied to the method for producing the copolymerized polyamide resin, and a melt polymerization method, a solution polymerization method, an interfacial polymerization method and the like are used.
  • monobasic acids such as acetic acid and benzoic acid, hexylamine, aniline
  • a monoacid base or the like as a molecular weight regulator.
  • heat stabilizers such as sodium phosphite, sodium hypophosphite, phosphorous acid, hypophosphite and hindered phenol, and other polymerization additives.
  • the copolymerization ratio represents the monomer charge ratio (molar ratio).
  • any organic solvent that can dissolve the curable binder resin in the present invention can be used.
  • alcohols having 5 or less carbon atoms such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol; black mouth form, 1,2-dichloroethane, dichloromethane, trichrene, carbon tetrachloride, 1,2-dichloropropane
  • Non-organic hydrocarbons such as dimethylformamide, etc .
  • aromatic hydrocarbons such as toluene, xylene, etc., but any combination of these and mixed solvent in any proportion Can be used.
  • the curable binder resin for the undercoat layer according to the present invention when used alone, is not dissolved. Even if it is an organic solvent, it can be used if it can melt
  • the total amount (solid content) of the curable binder resin and metal oxide particles used in the coating solution for forming the undercoat layer of the present invention and the content ratio of the organic solvent are as follows.
  • the coating method to be applied may be appropriately modified so that a uniform coating film is formed.
  • the coating liquid for forming the undercoat layer in Embodiments 1 and 2 in the present invention contains metal oxide particles, and the metal oxide particles are dispersed in the coating solution.
  • the method for dispersing the metal oxide particles in the coating solution is not particularly limited.For example, wet dispersion is performed in an organic solvent using a known mechanical grinding device such as a ball mill, a sand grind mill, a planetary mill, or a roll mill. Thus, the coating liquid for forming the undercoat layer can be produced. Among these, it is preferable to disperse using a dispersion medium.
  • any known dispersing device may be used, but preferable ones include a pebble mill, a ball mill, a sand mill, a screen mill, a gap mill, and a vibration mill. , Paint shakers, and attritors. Among these, those that can be dispersed by circulating the coating liquid are preferred. From the viewpoint of preferable dispersion efficiency, fineness of the reached particle size, ease of continuous operation, etc., wet stirring ball mills such as sand mills, screen mills, gap mills, etc. Is used. These mills may be either vertical or horizontal.
  • the disc shape of the mill can be any plate type, vertical pin type, horizontal pin type or the like.
  • a liquid circulation type sand mill is used.
  • the method for producing the coating liquid for forming the undercoat layer which is an embodiment 3 of the present invention, comprises metal oxide particles and
  • the metal oxide particles have an average particle size of 5 ⁇ m to 200 ⁇ m. It is characterized by using metal oxide particles dispersed using a dispersion medium. By dispersing using a dispersion medium having an average particle diameter of 5 ⁇ m to 200 m, a uniform dispersion can be obtained in a short time, and a dispersion having good dispersion stability can be obtained.
  • the average particle diameter of the dispersion media is excessively reduced, the mass of the dispersion media becomes too small, and efficient dispersion may not be possible.
  • the average particle size of the dispersion media is excessively increased, excessively large force is applied to the metal oxide particles, and the metal oxide particles may aggregate to form coarse oxide particle aggregates. .
  • the average particle is used as the dispersion media of the wet stirring ball mill. Force that the diameter must be 5 ⁇ m or more, preferably 10 ⁇ m or more. Moreover, although it is essential that it is 200 m or less, 100 m or less is preferable. Dispersion media with a small particle size tend to give a uniform dispersion in a short time. However, if the average particle size of the dispersion media becomes too small, the mass of the dispersion media will become too small to achieve efficient dispersion. There is a case.
  • Examples of the mill using a dispersion medium having an average particle diameter in the above range include a sand mill and a ball mill.
  • the "average particle size" of the dispersion medium in the embodiment 3 of the present invention is measured by image analysis. Since the dispersion media usually has a shape close to a true sphere, the average particle diameter can be obtained by measurement by image analysis.
  • the specific measuring device is:-The average particle size of the dispersion media was measured by an image analysis device called LUZ EX50 manufactured by Reco, and the "average particle size of the dispersion media" of the present invention was measured by the device. Define as a thing.
  • the true density of the dispersion medium is usually 5.5 gZcm 3 or more, preferably 5.9 gZcm 3 or more, more preferably 6. OgZcm 3 or more. In general, it is preferable to disperse using a higher-density dispersion medium because it tends to give a uniform dispersion in a short time.
  • the “true density” of the distributed media is defined as measured by the Archimedes method.
  • the sphericity of the dispersion medium is preferably 1.08 or less. 1. A dispersion medium having a sphericity of 07 or less is particularly preferable.
  • the “sphericity” of a distributed medium is defined as the value obtained by measuring the sphericity with an image analysis device called LUZ EX50 manufactured by Reco.
  • the material of the dispersion medium is insoluble in the coating solution for forming the undercoat layer and has a specific gravity greater than that of the coating solution for forming the undercoat layer, and reacts with the coating solution for forming the undercoat layer.
  • Any known dispersion medium can be used as long as it does not alter the coating solution for forming the undercoat layer.
  • steel balls such as chrome balls (ball balls for ball bearings), carbon balls (carbon steel balls); stainless steel balls; ceramic balls such as silicon nitride balls, silicon carbide, zirconium carbide, and alumina; titanium nitride, titanium carbonitride, etc.
  • Ceramic spheres are preferred, and in particular, zirconia fired balls are preferred. More specifically, it is particularly preferable to use the sintered zirconium beads described in Japanese Patent No. 3400836.
  • a production method in which the metal oxide particles are subjected to a dispersion treatment using a wet stirring ball mill is preferable in that a coating liquid with more excellent dispersibility can be produced efficiently.
  • the coating solution produced by the production method of Embodiment 3 of the present invention is not particularly limited, but the coating solution of Embodiment 1 or the coating solution of Embodiment 2 of the present invention is particularly preferable. Further, “a coating liquid which is the coating liquid of aspect 1 of the present invention and is also the coating liquid of aspect 2” manufactured by the manufacturing method of aspect 3 of the present invention is more preferable.
  • the metal oxide particles are excellent so as to have the volume average particle diameter Mv as in aspect 1 because the average particle diameter of the dispersion medium used for dispersion is relatively small. Can be distributed. Further, according to the production method of aspect 3, the average particle diameter of the dispersion medium used for dispersion is relatively small V, etc., so that the metal has a range of ⁇ represented by formula (1) in aspect 2.
  • the acid oxide particles can be well dispersed.
  • the wet stirring ball mill includes a cylindrical stator, a slurry supply port provided at one end of the stator, and a slurry supply port provided at the other end of the stator.
  • a rotor that stirs and mixes the slurry supplied from the discharge port, the medium filled in the stator and the supply port, and the rotor connected to the discharge port and rotates integrally with the rotor or independent of the rotor.
  • a wet stirring ball mill comprising a separator for separating the medium and the slurry by the action of centrifugal force and discharging the slurry from the discharge port.
  • a wet stirring ball mill that is a hollow discharge passage communicating with the discharge port is preferable.
  • the rotor is preferably of the pin, disk or wheeler type.
  • the slurry from which the media is separated by the separator is discharged through the shaft center. Since the centrifugal force does not act on the shaft center, the slurry has kinetic energy. However, it is discharged in the state. For this reason, kinetic energy is not wasted and useless power is not consumed.
  • Such a wet stirring ball mill may be horizontally oriented, but is preferably vertically oriented in order to increase the filling rate of the media, and a discharge port is provided at the upper end of the mill. It is also desirable to provide a separator above the media filling level.
  • the supply port is provided at the bottom of the mill.
  • the supply port is composed of a valve seat and a V-shaped, trapezoidal, or cone-shaped valve body that is fitted to the valve seat so as to be movable up and down and can be in line contact with the edge of the valve seat.
  • the raw slurry is supplied, but the media can be prevented from falling. To be. It is also possible to widen the slit to raise the valve body to discharge the media, or to lower the valve body to close the slit and seal the mill. Further, since the slit is formed by the edge of the valve body and the valve seat, even if the coarse particles in the raw material slurry are difficult to stagnate, they are likely to come out vertically and are not easily clogged.
  • the valve body is vibrated up and down by the vibration means, the coarse particles trapped in the slit can be removed from the slit, and the stagnation itself is difficult to occur.
  • the shearing force is applied to the raw material slurry by the vibration of the valve body to lower the viscosity, and the amount of raw material slurry passing through the slit, that is, the supply amount can be increased.
  • vibration means for vibrating the valve body in addition to mechanical means such as a vibrator, screws integrated with the valve body are used.
  • Means for changing the pressure of the compressed air acting on the ton such as a reciprocating compressor, an electromagnetic switching valve for switching the intake and exhaust of the compressed air, and the like can be used.
  • Such a wet stirring ball mill is also provided with a screen for separating the media at the bottom and a product slurry take-out port so that the product slurry remaining in the mill can be taken out after grinding. Desire! /
  • a particularly preferred wet stirring ball mill used in the manufacturing method of aspect 3 includes a cylindrical vertical stator, a product slurry supply port provided at the bottom of the stator, and a slurry discharge provided at the upper end of the stator. Stir and mix the outlet, the shaft that is pivotally supported by the upper end of the stator and rotationally driven by a driving means such as a motor, and the medium that is fixed to the shaft and filled in the stator and the slurry supplied from the supply port
  • a vertical type consisting of a pin, disk, or annular type rotor, a separator that is provided near the discharge port and separates the media from the slurry, and a mechanical seal that is provided on the bearing that supports the shaft at the top of the stator.
  • the lower part of the annular groove into which the O-ring fits is expanded downward by cutting and the clearance is widened, so that slurry and media enter and swallow or solidify. The clogging of the sealing ring will occur 1 and the mating ring will follow the sealing ring smoothly, and the mechanical seal function will be maintained.
  • the lower part of the fitting groove where the O-ring fits has a V-shaped cross section, and the whole is not thin, so the strength is not impaired and the holding function of the O-ring It will not be damaged.
  • the wet stirring ball mill includes a cylindrical stator, a slurry supply port provided at one end of the stator, a slurry discharge port provided at the other end of the stator, Stir and mix the media filled in the stator and the slurry supplied from the supply port.
  • the rotor is connected to the discharge port and rotates integrally with the rotor, or rotates independently from the port, and is separated into media and slurry by the action of centrifugal force.
  • a wet stirring ball mill comprising a separator for discharging the gas from the discharge port, the separator being fitted into the fitting groove and two discs having blade fitting grooves on the inner surfaces facing each other. It is preferable to have a blade interposed between the disks and a pressing means for holding the disk with the blade interposed from both sides.
  • the presser means is composed of a shaft step that forms a stepped shaft, and a cylindrical presser unit that fits the shaft and presses the disc, and includes a shaft step and a presser step.
  • the disk with the blade interposed is sandwiched and supported from both sides.
  • the rotor is preferably of the pin, disk or air type.
  • FIG. 1 shows an example of a vertical wet stirring ball mill that is particularly preferably used in Embodiment 3 of the present invention.
  • the raw slurry is supplied to a vertical wet stirring ball mill, pulverized by stirring with the media in the mill, and then separated by the separator 14 and discharged through the shaft 15 shaft. Then, it is designed to circulate and grind the return path.
  • a vertical wet stirring ball mill includes a stator 17 having a longitudinally cylindrical shape and a jacket 16 through which cooling water for powerful mill cooling is passed.
  • the shaft 15 is positioned at the shaft center of the shaft 7 and is rotatably supported at the upper part of the stator.
  • the shaft 15 is provided with a mechanical seal at the bearing portion, and the shaft center at the upper portion is a hollow discharge passage 19.
  • the separator 14 is composed of a pair of discs 31 fixed to the shaft 15 at a predetermined interval and a blade 32 connecting the discs 31 to form an impeller.
  • the centrifugal force is applied to the media and the slurry that have entered between the discs by rotating in the direction of the disk, and due to the difference in specific gravity, the media is blown outward in the radial direction, while the slurry is discharged through the discharge path 19 of the shaft 15 shaft center And then.
  • the raw material slurry supply port 26 includes an inverted trapezoidal valve body 35 that fits up and down on a valve seat formed on the bottom of the stator, and a bottomed cylindrical body 36 that projects downward from the bottom of the stator. That is, when the valve element 35 is pushed up by the supply of the raw slurry, an annular slit is formed between the valve seat and the raw slurry, and the raw slurry is supplied into the mill.
  • valve body 35 When the raw material is supplied, the valve body 35 rises against the pressure in the mill due to the supply pressure of the raw material slurry fed into the cylindrical body 36, and forms a slit with the valve seat. In order to eliminate clogging at the slit, the valve body 35 is repeatedly moved up and down to the upper limit position in a short cycle so that clogging can be eliminated.
  • the vibration of the valve body 35 may be performed at all times, or may be performed when the raw material slurry contains a large amount of coarse particles, or when the supply pressure of the raw material slurry increases due to clogging. Even if it is done in conjunction with.
  • the mechanical seal is formed by pressing the mating ring 101 on the stator side to the seal ring 100 fixed to the shaft 15 by the action of the panel 102, and mating with the stator 17 Sealing with the ring 101 is performed by an O-ring 104 fitted in the fitting groove 103 on the stator side.
  • a taper-shaped notch (not shown) that expands downward is formed in the lower part of the O-ring fitting groove 103, and between the lower part of the fitting groove 103 and the mating ring 101.
  • the minimum clearance a has a narrow length a, so that media and slurry can enter and solidify, preventing the movement of the mating ring 101 and preventing the seal ring 100 from being damaged.
  • the rotor 21 and the separator 14 are fixed to the same shaft 15.
  • the rotor 21 and the separator 14 are fixed to separate shafts arranged on the same axis and are driven to rotate separately.
  • the structure is simple because only one drive device is required.
  • the rotor and the shaft are attached to separate shafts, and the drive is separated.
  • the rotor and the separator can be driven to rotate at optimum rotational speeds. In the ball mill shown in FIG.
  • the shaft 105 is a stepped shaft
  • the separator 106 is inserted from the lower end of the shaft, and then the spacer 107 and the disk or pin-shaped rotor 108 are alternately inserted
  • a stopper 109 is fixed to the lower end of the shaft with a screw 110
  • a separator 106, a spacer 107 and a rotor 108 are sandwiched and connected and fixed by a step 105a of the shaft 105 and the stopper 109.
  • the separator 106 includes a pair of disks 115 each having a blade fitting groove 114 formed on the inner surface thereof, and a blade 116 interposed between the two disks and fitted in the blade fitting groove 114.
  • the two discs 115 are maintained at a constant interval, and an impeller is constituted by an annular spacer 113 having a hole 112 communicating with the discharge passage 111 as shown in FIG.
  • wet stirring ball mill having such a structure examples include an ultra apex mill manufactured by Kotobuki Industries Co., Ltd.
  • the ball mill stator 17 is filled with media and driven by external power to rotate the rotor 21 and the separator 14, while a certain amount of raw slurry is sent to the supply port 26, thereby the edge of the valve seat. It is fed into the mill through a slit formed between the valve body 35.
  • the raw slurry and media in the mill are agitated and mixed by the rotation of the rotor 21 to pulverize the slurry, and the rotation of the separator 14 separates the media and the slurry that have entered the separator due to the difference in specific gravity. While the heavy media is blown outward in the radial direction, the slurry having a low specific gravity is discharged through the discharge path 19 formed in the shaft center of the shaft 15 and returned to the raw material tank.
  • the pulverization has progressed to some extent, the particle size of the slurry is appropriately measured. When the desired particle size is reached, the raw material pump is stopped once, then the mill operation is stopped, and the pulverization is terminated.
  • the filling rate of the medium filled in the mill is 50% to: L00%. More preferably, it is 70% to 95%, particularly preferably 80% to 90%.
  • the wet stirring ball mill applied to disperse the coating solution for forming the undercoat layer according to the present invention may be of the impeller type although the separator may be a screen or a slit mechanism. Is preferably the desired vertical type.
  • the force required to place the wet stirring ball mill in a vertical orientation and a separator on the upper part of the mill Especially when the media filling rate is set to 80% to 90%, grinding is most efficient and the separator is set to the media filling level. This makes it possible to prevent the medium from being ejected on the separator.
  • the operation conditions of the wet stirring ball mill applied to disperse the metal oxide particles in the embodiment 3 of the present invention are the volume average particle diameter Mv of the metal oxide particles in the coating liquid, the coating liquid The surface shape of the undercoat layer formed by coating and forming the coating solution, and the characteristics of the electrophotographic photosensitive member having the undercoat layer formed by coating and applying the coating solution.
  • the supply speed of the coating liquid and the rotational speed of the rotor can be cited as having a great influence.
  • the supply speed of the coating liquid for forming the undercoat layer is related to the time during which the coating liquid for forming the undercoat layer stays in the mill. Therefore, the force affected by the volume of the mill and its shape is usually used.
  • the range of 20 kgZ hours to 80 kgZ hours is preferred per liter of mill volume (hereinafter sometimes abbreviated as “1 L”), more preferably 30 kg / hour to 70 kgZ hours per liter of mill volume. It is a range.
  • the rotational speed of the rotor is the force affected by parameters such as the rotor shape and the gap with the stator.
  • the peripheral speed of the rotor tip is 5 mZ to 20 mZ sec.
  • the range is preferably in the range of 8 mZ seconds to 15 mZ seconds, and more preferably in the range of 10 mZ seconds to 12 mZ seconds.
  • the dispersion medium is usually used in a volume ratio of 0.5 to 5 times the coating solution for forming the undercoat layer.
  • a dispersion aid that can be easily removed after dispersion can be used in combination.
  • the dispersion aid include sodium chloride and sodium nitrate.
  • the dispersion of the metal oxide is preferably carried out in the presence of a dispersion solvent in a wet manner, but a curable noinder resin and various additives may be mixed at the same time.
  • the solvent is not particularly limited, but the use of the organic solvent is preferable because it is not necessary to go through steps such as solvent exchange after dispersion. Any one of these solvents may be used alone, or two or more may be used in combination as a mixed solvent.
  • the amount of the organic solvent used is 1 weight of metal oxide particles to be dispersed.
  • the amount is usually 0.1 parts by weight or more, preferably 1 part by weight or more, and usually 500 parts by weight or less, preferably 100 parts by weight or less.
  • the temperature during mechanical dispersion can be from the freezing point of the solvent (or mixed solvent) to the boiling point or less, but from the viewpoint of safety during production, it is usually 10 ° C or more and 200 ° C. It is performed in the following range.
  • Ultrasonic treatment applies ultrasonic vibration to the coating solution for forming the undercoat layer, but there is no particular limitation on the vibration frequency, etc.
  • the ultrasonic wave is supersonic with an oscillator of 10 kHz to 40 kHz, preferably 15 kHz to 35 kHz. Apply sonic vibration.
  • the output of the ultrasonic oscillator There is no particular limitation on the output of the ultrasonic oscillator, but a power of 100W to 5kW is usually used.
  • the amount of the undercoat layer forming coating solution to be processed at a time is preferably 1L to 50L, more preferably 5L to 30L, and particularly preferably 10L to 20L.
  • the output of the ultrasonic oscillator is preferably 200 W to 3 kW, more preferably 300 W to 2 kW, and particularly preferably 500 W to 1.5 kW.
  • the method of applying ultrasonic vibration to the coating solution for forming the undercoat layer is not particularly limited, but the method of directly immersing the ultrasonic oscillator in the container containing the coating solution for forming the undercoat layer, the undercoat layer A method of bringing an ultrasonic oscillator into contact with the outer wall of a container containing a forming coating liquid, a method of immersing a container containing a coating liquid for forming an undercoat layer in a liquid that has been vibrated by an ultrasonic oscillator, etc. Is mentioned.
  • a method of immersing a solution containing an undercoat layer forming coating solution in a liquid to which vibration is applied by an ultrasonic oscillator is preferably used.
  • liquids that can be vibrated by an ultrasonic vibrator include water; alcohols such as methanol; aromatic hydrocarbons such as toluene; and fats and oils such as silicone oil. Considering the properties, cost, cleanability, etc., it is preferable to use water.
  • the efficiency of ultrasonic treatment changes depending on the temperature of the liquid. It is preferable to keep it constant.
  • the temperature of the liquid to which vibration is applied rises due to the applied ultrasonic vibration. There is.
  • the temperature of the liquid is usually 5 ° C to 60 ° C, preferably 10 ° C to 50 ° C, more preferably 15 ° C to 40 ° C! I like it!
  • a container for storing a coating solution for forming an undercoat layer during ultrasonic treatment it is usually used to contain a coating solution for forming an undercoat layer used for forming a photosensitive layer for an electrophotographic photoreceptor.
  • Any container may be used as long as it is a container that can be used, but examples thereof include a resin container such as polyethylene and polypropylene, a glass container, and a metal can.
  • metal cans are preferred, and 18 liter metal cans are preferably used as specified in JIS Z 1602. This is because it is strong against impacts that are hardly affected by organic solvents.
  • the coating liquid for forming the undercoat layer is used after being filtered as necessary in order to remove coarse particles.
  • a filtration medium in this case, any filtration medium such as cellulose fiber, rosin fiber, glass fiber or the like usually used for filtration may be used.
  • a so-called wind filter in which various fibers are wound around a core material is preferable because of a large filtration area and high efficiency.
  • the core material any conventionally known core material can be used.
  • a stainless steel core material, a core material made of resin not dissolved in a coating solution for forming an undercoat layer such as polypropylene, and the like can be used.
  • the coating solution for forming the undercoat layer thus produced is used for forming an undercoat layer by further adding a binder, various auxiliary agents, and the like as desired.
  • the undercoat layer according to the present invention comprises a coating solution for forming an undercoat layer on a support, such as dip coating, spray coating, nozzle coating, spiral coating, ring coating, bar coating coating, roll coating coating, blade coating, etc. It is formed by coating by a known coating method and drying.
  • Spray coating methods include air spray, airless spray, electrostatic air spray, electrostatic airless spray, rotary atomizing electrostatic spray, hot spray, hot airless spray, etc.
  • the degree of adhesion, adhesion efficiency, etc. in the rotary atomization type electrostatic spray, it is disclosed in the republished Japanese Laid-Open Patent Publication No. 1-805198, and the axial direction of the cylindrical workpiece while rotating it.
  • the total solid concentration of the coating solution for forming the undercoat layer is usually 1% by weight or more, preferably 10% by weight or more, and usually 80% by weight or less, preferably 50%.
  • the viscosity is in the range of% by weight or less, and the viscosity is preferably in the range of 0.1 lcps or more, and preferably in the range of lOOcps or less.
  • the coating film is dried, and the temperature and time are adjusted so that necessary and sufficient drying and curing are performed.
  • the drying temperature is usually in the range of 100 ° C to 250 ° C, preferably 120 ° C to 180 ° C.
  • a hot air dryer, a steam dryer, an infrared dryer and a far infrared dryer can be used.
  • thermosetting resin since a curable binder resin is used, it is preferable to perform the drying and curing simultaneously.
  • drying and thermosetting can be performed at the same time, and the time, temperature, etc. are determined according to the conditions and temperature of the resin used in the same manner as above. , Time, etc.).
  • the curing time is from 10 minutes to 3 hours, and considering the productivity, which is preferably 30 minutes or more in view of curability, it is preferably 2 hours or less.
  • An electrophotographic photosensitive member having an undercoat layer formed by coating and forming the coating liquid of aspect 1 or aspect 2 of the present invention, or an undercoat layer forming coating liquid produced by the production method of aspect 3 The electrophotographic photosensitive member having the undercoat layer thus formed has stable electric characteristics even at low temperature and low humidity.
  • the photosensitive layer of the electrophotographic photoreceptor according to the present invention includes an undercoat layer on a conductive support. It has a photosensitive layer, and the undercoat layer is provided between the conductive support and the photosensitive layer.
  • a photosensitive layer any constitution applicable to a known electrophotographic photosensitive member can be adopted. Specifically, for example, a photoconductive material is simply dissolved or dispersed in a binder resin.
  • a photoconductive material exhibits the same performance as a function regardless of whether it is a single layer type or a laminated type.
  • the photosensitive layer of the electrophotographic photosensitive member according to the present invention may be in any known form, but comprehensively taking into account the mechanical properties, electrical characteristics, manufacturing stability, etc. of the photosensitive member. More preferred is a laminated type photoreceptor, more preferred is a forward laminated type photoreceptor in which an undercoat layer, a charge generation layer and a charge transport layer are laminated in this order on a conductive support.
  • the conductive support examples include a metal material such as aluminum, aluminum alloy, stainless steel, copper, and nickel, and a resin material imparted with conductivity by adding conductive powder such as metal, carbon, and tin oxide.
  • resin, glass, paper, or the like obtained by depositing or coating a conductive material such as aluminum, nickel, ITO (indium tin oxide alloy) on its surface is mainly used.
  • a drum shape, a sheet shape, a belt shape or the like is used.
  • a conductive material with an appropriate resistance value may be coated on a conductive support made of a metal material to control conductivity and surface properties, or to cover defects.
  • a metal material such as an aluminum alloy
  • it may be used after anodizing.
  • an anodic oxidation film is formed by anodizing in an acidic bath of chromic acid, sulfuric acid, oxalic acid, boric acid, sulfamic acid, etc., but anodizing treatment in sulfuric acid is better. Give the result.
  • sulfuric acid concentration is 100gZL ⁇ 300gZL
  • dissolved aluminum concentration is 2gZL ⁇ 15gZL
  • liquid temperature is 15 ° C ⁇ 30 ° C
  • electrolysis voltage is 10V ⁇ 20V
  • current density is 0.5AZdm 2 It is preferably set within the range of ⁇ 2AZdm 2 , but is not limited to the above conditions.
  • the sealing process may be performed by a known method.
  • nickel fluoride as the main component It is preferable to perform a low temperature sealing treatment soaked in an aqueous solution containing water, or a certain high temperature sealing treatment soaked in an aqueous solution containing nickel acetate as a main component.
  • concentration of the nickel fluoride aqueous solution used in the case of the low-temperature sealing treatment can be selected as appropriate, but more preferable results can be obtained when it is used in the range of 3 gZ L to 6 gZL.
  • the treatment temperature is usually 25 ° C or higher, preferably 30 ° C or higher, and usually 40 ° C or lower, preferably 35 ° C or lower.
  • the aqueous solution of nickel fluoride is usually 4.5 or more, preferably 5.5 or more, and usually 6.5 or less, preferably 6.0 or less.
  • As the pH regulator oxalic acid, boric acid, formic acid, acetic acid, sodium hydroxide, sodium acetate, aqueous ammonia and the like can be used.
  • the treatment time is preferably 1 to 3 minutes per 1 ⁇ m of film thickness.
  • cobalt fluoride, cobalt acetate, nickel sulfate, a surfactant or the like may be added to the nickel fluoride aqueous solution. Next, it is washed with water and dried to finish the low-temperature sealing treatment.
  • an aqueous solution of a metal salt such as nickel acetate, cobalt acetate, lead acetate, nickel acetate cobalt, and barium nitrate can be used, but it is particularly preferable to use nickel acetate. ⁇ .
  • the concentration of nickel acetate aqueous solution is preferably 5 g / L to 20 g / L.
  • the treatment temperature is usually 80 ° C or higher, preferably 90 ° C or higher, and usually 100 ° C or lower, preferably 98 ° C or lower, and the pH of the aqueous nickel acetate solution is 5.0 to 6.0. It is preferable to treat with a range.
  • ammonia water, sodium acetate, or the like can be used as the pH regulator.
  • the treatment time is 10 minutes or longer, preferably 15 minutes or longer.
  • sodium acetate, organic carboxylic acid, ionic surfactant, nonionic surfactant, etc. may be added to the nickel acetate aqueous solution in order to improve the film properties. Further, it may be treated with high temperature water or high temperature steam substantially free of salts. Next, it is washed with water and dried to finish the hot sealing process.
  • the average film thickness of the anodic acid coating is thick, a strong sealing condition is required due to the high concentration of the sealing liquid and high temperature for a long time. Therefore, productivity is deteriorated and surface defects such as spots, dirt, and dusting are easily generated on the coating surface. For this reason, the average thickness of the anodized coating is usually 20 m or less, particularly 7 m or less. It is preferable.
  • the surface of the support may be smooth, or may be roughened by using a special cutting method or polishing. Further, it may be roughened by mixing particles having an appropriate particle size with the material constituting the support.
  • the drawing tube can be used as it is without cutting.
  • the treatment eliminates dirt and foreign matter deposits on the surface, small scratches, etc., resulting in a uniform and clean support. Preferable because it is obtained.
  • the thickness of the undercoat layer can be selected arbitrarily, but is usually preferably in the range of 0.1 ⁇ m to 20 ⁇ m from the viewpoint of improving the photoreceptor characteristics and coating properties. Particularly preferred is the range of 0.2 m to 18 / ⁇ ⁇ . Further, a known anti-oxidation agent or the like may be added to the undercoat layer.
  • the surface shape of the undercoat layer according to the present invention is not particularly limited, but the in-plane root mean square roughness is not particularly limited.
  • RMS is usually in the range of 10 nm to 100 nm, preferably in the range of 20 nm to 50 nm.
  • the in-plane arithmetic average roughness (Ra) of the undercoat layer according to the present invention is usually ⁇ ! It is in the range of ⁇ lOOnm, preferably in the range of 20nm to 50nm.
  • the in-plane maximum roughness (P ⁇ V) of the undercoat layer according to the present invention is usually in the range of 100 nm to 1000 nm, preferably in the range of 300 nm to 800 nm.
  • In-plane Root Mean Square Roughness is the root mean square roughness of Z (X) and in-plane arithmetic mean roughness (Ra) Is the average of the absolute values of Z (x), and in-plane maximum roughness (PV) is the sum of the maximum value of the peak height and the maximum value of the valley depth of Z (x).
  • the numerical values of these surface shapes are defined as those measured by a method of detecting irregularities on the sample surface by combining a high-accuracy phase shift detection method and interference fringe order counting using an optical interference microscope. The Specifically, it is defined as that measured in the Wave mode by the interference fringe addressing method using the Micromap manufactured by Ryoji System.
  • the regular reflectance ratio of the undercoat layer in the present invention is not particularly limited, but the following range is preferred.
  • the “regular reflectance ratio” refers to the regular reflectance of the undercoat layer on the conductive support relative to the regular reflectance of the conductive support. Since the reflectivity ratio varies depending on the thickness of the undercoat layer, it is defined as the reflectivity ratio when the undercoat layer is 2 m.
  • the undercoat layer of the electrophotographic photosensitive member according to the present invention has a thickness of 2 m when the refractive index of the metal oxide particles contained in the undercoat layer is 2.0 or more.
  • the refractive index of the metal oxide particles is 2.0 or less
  • the regular reflection rate with respect to light having a wavelength of 400 nm of the conductive support converted to the case where the undercoat layer is 2 m the ratio of the regular reflectance to the light with a wavelength of 400 nm of the undercoat layer (reflectance ratio) is preferably 50% or more.
  • the undercoat layer contains a plurality of types of metal oxide particles having a refractive index of 2.0 or more, it contains a plurality of types of metal oxide particles having a refractive index of 2.0 or less. Even in such a case, the one having the same regular reflectance ratio as described above is preferable.
  • the refractive index is 2.0 or more.
  • the wavelength of the undercoat layer relative to the regular reflectance of the conductive support with respect to light having a wavelength of 480 nm, converted when the undercoat layer is 2 m.
  • the ratio of specular reflectance to 480 nm light (reflectance ratio) is particularly preferably 50% or more! /.
  • the thickness of the undercoat layer is not limited to 2 m, and may be any film thickness.
  • the electrophotographic photosensitive member is formed using the undercoat layer forming coating solution used for forming the undercoat layer of the electrophotographic photosensitive member.
  • a subbing layer having a thickness can be applied and formed on a conductive support equivalent to the body, and the regular reflectance can be measured on the subbing layer.
  • the regular reflectance ratio of the undercoat layer of the electrophotographic photosensitive member is measured and converted when the film thickness is 2 / zm.
  • the amount of decrease in light intensity after passing through dL is considered to be proportional to the light intensity I and dL before passing through the layer, and can be written as follows (k is a constant) .
  • Equation (1) is the same as that called Lambert's law in the solution system, and can be applied to the measurement of the reflectance in the present invention.
  • the regular reflectance ratio in the present invention uses the reflected light of the incident light to the conductive support as the denominator, so
  • the light that has reached the surface of the conductive support according to the formula (F) is regularly reflected after being multiplied by the reflectance R, and again passes through the optical path length L and exits to the surface of the undercoat layer. That is,
  • the optical path length is a force of 4 m in a round trip.
  • the reflectivity T of the undercoat layer on the arbitrary conductive support T is the film of the undercoat layer. It is a function of the thickness L (in this case, the optical path length is 2L) and is expressed as T (L). From equation (H)
  • T (2) T (L) 2 / L (K)
  • the reflectance when the undercoat layer is 2 m is measured by measuring the reflectance ratio T (L) of the undercoat layer.
  • the ratio T (2) can be estimated with considerable accuracy.
  • the thickness L of the undercoat layer is measured with an optional film thickness measuring device such as a roughness meter.
  • any material that has been proposed for use in the present application can be used.
  • examples of such substances are azo pigments, phthalocyanine pigments, anthanthrone pigments, quinacridone pigments, cyanine pigments, pyrylium pigments, thiapyrylium pigments, indigo pigments, polycyclic quinone pigments, Examples include squaric pigments.
  • Particularly preferred are phthalocyanine pigments and azo pigments.
  • Phthalocyanine pigments provide a photosensitive material with high sensitivity to laser light with a relatively long wavelength, and azo pigments have sufficient sensitivity to white light and laser light with a relatively short wavelength. In terms of having each, it speaks excellently.
  • a phthalocyanine compound when used as the charge generation material, a high effect is shown and preferable.
  • the phthalocyanine compound include metal-free phthalocyanine, metals such as copper, indium, gallium, tin, titanium, zinc, vanadium, silicon, and germanium, or oxides, halides, hydroxides, alkoxides thereof, and the like.
  • high-sensitivity crystal type X-type, metal-free phthalocyanine such as vertical type, A-type (also known as
  • Ruphthalocyanine also known as oxytitanium phthalocyanine
  • vanadyl phthalocyanine black-indium phthalocyanine
  • black-type black-type gallium phthalocyanine V-type hydroxygallium phthalocyanine
  • G-type I-type ⁇ Oxo gallium phthalocyanine dimer, type II, etc.
  • a mer is preferred.
  • these phthalocyanines A-type (
  • phthalocyanine compounds CuK o; oxytitanium that exhibits the Bragg angle (20 ⁇ 0.2 °) force of the X-ray diffraction spectrum for characteristic X-rays and the main diffraction peak at 27.3 ° Phthalocyanine, 9.3 °, 13.2 °, 26.2 °, 27.1 °, oxytitanium phthalocyanine showing main diffraction peaks at 9.2 °, 9.2, 14.1, 15.3, 19 7, 2 7.1.
  • a black-opened gallium phthalocyanine having diffraction peaks at 16.6 °, 25.5 °, and 28.3 ° is preferred.
  • oxytitanium phthalocyanine having a main diffraction peak at 27.3 ° is particularly preferred.
  • an oxytitanium having a main diffraction peak at 9.5 °, 24.1 °, and 27.3 ° is preferred.
  • Titanium phthalocyanine is particularly preferred.
  • the phthalocyanine-based compound only a single compound may be used, and V, some mixture, or a mixed crystal state may be used.
  • the mixed or mixed crystal state of the phthalocyanine compound here, the respective constituent elements may be mixed and used later, or mixed in the manufacturing process of phthalocyanine compound such as synthesis, pigmentation, and crystallization. It may be the one that caused the condition.
  • acid paste treatment, “grinding treatment”, solvent treatment and the like are known.
  • two kinds of crystals are mixed, mechanically ground and made amorphous, and then a specific crystal is obtained by solvent treatment. There is a method of converting to a state.
  • a charge generating substance other than the phthalocyanine compound may be used.
  • azo pigments perylene pigments, quinacridone pigments, polycyclic quinone pigments, indigo pigments, benzimidazole pigments, pyrylium salts, thiapyrylium salts, squalium salts, and the like can be used.
  • the charge generation material is dispersed in the coating solution for forming the photosensitive layer, and is dispersed in the coating solution. Before being crushed, it may be pre-ground. Pre-grinding is a force that can be performed using various apparatuses. Usually, a ball mill, a sand grind mill, or the like is used. Any pulverizing medium can be used as the pulverizing medium to be introduced into these pulverizing apparatuses as long as the pulverizing medium is not pulverized and can be easily separated after the dispersion process. Examples include beads and balls such as glass, anolemina, zirco-a, stainless steel, and ceramics.
  • the volume average particle diameter is 500 m or less, and more preferably 250 m or less.
  • the volume average particle diameter may be measured by any method commonly used by those skilled in the art, but is usually measured by a sedimentation method or a centrifugal sedimentation method.
  • the charge transport material examples include polymer compounds such as polyvinyl carbazole, polyburpyrene, polyglycidyl carbazole, and polyacenaphthylene; polycyclic aromatic compounds such as pyrene and anthracene; indole derivatives, imidazole derivatives, and force rubazole derivatives. , Heterocyclic compounds such as pyrazole derivatives, pyrazoline derivatives, oxadiazole derivatives, oxazole derivatives, thiadiazole derivatives; p Jetylaminobens aldehyde H, N, N diphenylhydrazone, N-methylcarbazole 3-carbaldehyde, N, N diphenylhydrazone, etc.
  • polymer compounds such as polyvinyl carbazole, polyburpyrene, polyglycidyl carbazole, and polyacenaphthylene
  • polycyclic aromatic compounds such as pyrene and anthracene
  • a hydrazone derivative, a strong rubazole derivative, a styryl compound, a butadiene compound, a triarylamine compound, a benzidine compound, or a compound in which a plurality of these are bonded is preferably used.
  • These charge transport materials may be used alone or in combination.
  • the photosensitive layer according to the electrophotographic photoreceptor of the present invention is formed in a form in which a photoconductive material is bound with various binder resins.
  • a photoconductive material is bound with various binder resins.
  • the Noinder resin any known binder resin that can be used for an electrophotographic photosensitive member can be used.
  • the layer containing the charge generation material is usually a charge generation layer, but may be contained in the charge transport layer.
  • the charge generation material usage ratio is usually in the range of 30 parts by weight to 500 parts by weight with respect to 100 parts by weight of Noinda resin contained in the charge generation layer. More preferably, it is 50 parts by weight to 300 parts by weight. If the amount of the charge generating material used is too small, the electrical characteristics as an electrophotographic photoreceptor will not be sufficient, and if it is too large, the stability of the coating solution will be impaired.
  • the volume average particle diameter of the charge generation material in the layer containing the charge generation material is preferably 1 ⁇ m or less, more preferably 0.5 m or less.
  • the film thickness of the charge generation layer is usually from 0.1 ⁇ to 2 / ⁇ m, preferably from 0.15 ⁇ m to 0.8 ⁇ m.
  • plasticizers for improving film formability, flexibility, mechanical strength, etc. additives for suppressing residual potential, dispersion aids for improving dispersion stability, It may contain leveling agents, surfactants, silicone oils, fluorine oils and other additives to improve coatability.
  • the charge generating material is dispersed in a matrix mainly composed of a binder resin and a charge transporting material having the same mixing ratio as the charge transporting layer described later.
  • the particle size of the charge generation material must be sufficiently small, and the volume average particle size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less. If the amount of the charge generating material dispersed in the photosensitive layer is too small, sufficient sensitivity can be obtained. If the amount is too large, there are harmful effects such as a decrease in chargeability and a decrease in sensitivity.
  • the photosensitive layer of a single-layer type photoreceptor also has a known plasticizer for improving film formability, flexibility and mechanical strength, an additive for suppressing residual potential, and an improvement in dispersion stability. It may contain dispersion aids, leveling agents to improve coating properties, surfactants, silicone oils, fluorine oils and other additives.
  • the charge transport layer may be formed of a single resin having a charge transport function, but the charge transport material is dispersed or dissolved in the binder resin. More preferred.
  • a structure in which the charge transport material is dispersed or dissolved in the binder resin is used as a matrix in which the charge generation material is dispersed.
  • binder resin used in the layer containing the charge transport material examples include vinyl polymers such as polymethyl methacrylate, polystyrene, polyvinyl chloride, and copolymers thereof, polycarbonate, polyarylate, polyester, Examples thereof include polyester carbonate, polysulfone, polyimide, phenoxy, epoxy, silicone resin, and these partially crosslinked cured products can also be used.
  • the layer containing the charge transport material may contain an antioxidant such as a hindered phenol or hindered amine, an ultraviolet absorber, a sensitizer, a leveling agent, an electron-withdrawing material, if necessary.
  • an antioxidant such as a hindered phenol or hindered amine, an ultraviolet absorber, a sensitizer, a leveling agent, an electron-withdrawing material, if necessary.
  • Various additives may be included.
  • the thickness of the layer containing the charge transport material is usually 5 ⁇ to 60; ⁇ ⁇ , preferably 10 111 to 45 111, more preferably 13 ⁇ to 27; ⁇ m.
  • the ratio of the Noinda resin and the charge transport material is usually in the range of 20 parts by weight to 200 parts by weight, preferably 30 parts by weight to 150 parts by weight, with respect to 100 parts by weight of the binder resin. Is used in the range of 40 to 120 parts by weight.
  • a conventionally known surface protective layer or overcoat layer mainly composed of, for example, a thermoplastic or thermosetting polymer may be provided.
  • a coating solution obtained by dissolving or dispersing a substance contained in a layer in a solvent such as a coating solution for forming an undercoat layer of the present invention
  • a coating solution for forming an undercoat layer of the present invention is prepared by, for example, a dip coating method, a spray coating method, They are sequentially applied and formed using a known method such as a ring application method.
  • various additives such as a leveling agent, an antioxidant, and a sensitizer may be included to improve the coating properties as necessary.
  • Preferred examples of the organic solvent used in the coating solution for forming the photosensitive layer include, for example, alcohols such as methanol, ethanol, propanol, 1-hexanol, 1,3 butanediol; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone and cyclohexanone; Ethers such as dioxane, tetrahydrofuran, and ethylene glycol monomethyl ether; Ether ketones such as 4-methoxy 4 methyl 2 pentanone; benzene, toluene, xylene, black benzene, etc.
  • alcohols such as methanol, ethanol, propanol, 1-hexanol, 1,3 butanediol
  • acetone methyl ethyl ketone
  • Ketones such as methyl isobutyl ketone and cyclohexanone
  • Ethers such as dioxan
  • aromatic hydrocarbons aromatic hydrocarbons
  • esters such as methyl acetate and ethyl acetate
  • amides such as N, N dimethylformamide and N, N dimethylacetamide
  • sulfoxides such as dimethyl sulfoxide.
  • alcohols, aromatic hydrocarbons, ethers and ether ketones are particularly preferred. More preferable examples include tonolene, xylene, 1-hexanol, 1,3 butanediol, tetrahydrofuran, 4-methoxy-4-methyl-2-pentanone, and the like.
  • solvents such as 1,2-dimethoxyethane, among which ethers, alcohols, amides, sulfoxides, ethers, ketones, amides and sulphoxides are suitable, 1 Alcohols such as propanol are suitable. Particularly preferably, ethers are mixed.
  • the phthalocyanine has surface powers such as crystal form stabilizing ability and dispersion stability.
  • the image forming apparatus includes an electrophotographic photosensitive member 1, a charging device 2, an exposure device 3, a developing device 4, and a transfer device 5, and further, if necessary, a cleaning device. 6 and a fixing device 7 are provided.
  • an electrophotographic photosensitive member, charging means for charging the photosensitive member, and image exposure to the charged photosensitive member are performed to form an electrostatic latent image.
  • An image forming apparatus comprising: an exposure unit; a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target.
  • An image forming apparatus using a body comprising: an exposure unit; a developing unit that develops the electrostatic latent image with toner; and a transfer unit that transfers the toner to a transfer target.
  • the electrophotographic photosensitive member 1 is not particularly limited as long as it is the above-described electrophotographic photosensitive member of the present invention.
  • Fig. 3 as an example, the photosensitive layer described above is formed on the surface of a cylindrical conductive support. This shows a drum-shaped photoconductor formed.
  • a charging device 2, an exposure device 3, a developing device 4, a transfer device 5 and a cleaning device 6 are arranged along the outer peripheral surface of the electrophotographic photosensitive member 1, respectively.
  • the charging device 2 charges the electrophotographic photoreceptor 1, and uniformly charges the surface of the electrophotographic photoreceptor 1 to a predetermined potential.
  • a roller type charging device (charging roller) is shown as an example of the charging device 2.
  • a corona charging device such as a corotron and a scorotron
  • a contact charging device such as a charging brush, and the like are often used. In the present invention, this configuration is desirable because the effect is remarkably exhibited when the charging means is disposed in contact with the electrophotographic photosensitive member.
  • the electrophotographic photosensitive member 1 and the charging device 2 are designed to be removable from the main body of the image forming apparatus as a cartridge including both of them (hereinafter referred to as an "electrophotographic cartridge" as appropriate). In the present invention, it is desirable to use it in such a form.
  • another aspect of the present invention includes at least an electrophotographic photosensitive member, a charging unit that charges the photosensitive member, and a developing unit that develops an electrostatic latent image formed on the photosensitive member with toner.
  • An electrophotographic cartridge having the above-mentioned photoconductor It is a photo cartridge.
  • the exposure and charging repetition characteristics under low temperature and low humidity are not stable, and the resulting image has black spots and color spots.
  • image defects such as the above occur frequently, and clear and stable image formation cannot be performed as an image forming apparatus or an electrophotographic cartridge.
  • this configuration is desirable since the effect is remarkably exhibited when the charging means is disposed in contact with the electrophotographic photosensitive member.
  • the electrophotographic cartridge can be removed from the main body of the image forming apparatus, and another new U ⁇ electrophotographic cartridge can be mounted on the main body of the image forming apparatus. It ’s like that.
  • the toner described later is often stored in the toner cartridge and designed to be removable from the main body of the image forming apparatus. When the toner in the used toner cartridge runs out, the toner cartridge is removed. It can be removed from the main body of the image forming apparatus and another new toner cartridge can be installed. Further, the electrophotographic photosensitive member 1, the charging device 2, and a cartridge provided with all of the toner may be used.
  • the type of the exposure apparatus 3 is not particularly limited as long as it can expose the electrophotographic photosensitive member 1 to form an electrostatic latent image on the photosensitive surface of the electrophotographic photosensitive member 1.
  • Specific examples include halogen lamps, fluorescent lamps, lasers such as semiconductor lasers and He-Ne lasers, and LEDs.
  • exposure may be performed by a photoconductor internal exposure method.
  • the light used for the exposure is arbitrary.
  • the exposure may be performed with monochromatic light with a wavelength of 780 nm, monochromatic light with a wavelength slightly shorter than 600 nm to 700 nm, or monochromatic light with a short wavelength of 350 nm to 600 nm. .
  • the wavelength is 380 ⁇ ! It is preferable to expose with monochromatic light having a short wavelength of ⁇ 600 nm, and more preferably with monochromatic light having a wavelength of 380 nm to 500 nm.
  • the developing device 4 any device such as a cascade development, a one-component conductive toner image, a two-component magnetic brush development, or a dry development method or a wet development method can be used.
  • the developing device 4 includes a developing tank 41, an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and stores toner T inside the developing tank 41. It has become the composition which is.
  • a replenishing device (not shown) for replenishing toner T may be attached to the developing device 4 as necessary. This replenishing device is configured to replenish toner T from a container such as a bottle or a cartridge.
  • the supply roller 43 is formed of a conductive sponge or the like.
  • the developing roller 44 also has a metal roll such as iron, stainless steel, aluminum, or nickel, or a resin roll having such a metal roll coated with silicone resin, urethane resin, fluorine resin, or the like. If necessary, the surface of the developing roller 44 may be smoothed or roughened.
  • the developing roller 44 is disposed between the electrophotographic photosensitive member 1 and the supply roller 43 and is in contact with the electrophotographic photosensitive member 1 and the supply roller 43, respectively.
  • the supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism (not shown).
  • the supply roller 43 carries the stored toner T and supplies it to the developing roller 44.
  • the developing roller 44 carries the toner T supplied by the supply roller 43 and contacts the surface of the electrophotographic photoreceptor 1.
  • the regulating member 45 is made of a resin blade made of silicone resin, urethane resin, etc., a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, etc., or such metal blade is coated with resin. Formed by a blade or the like.
  • the regulating member 45 is in contact with the developing roller 44 and is pressed against the developing roller 44 side with a predetermined force by a spring or the like (general blade linear pressure is 5 gZcm to 500 gZcm). If necessary, the regulating member 45 may be provided with a function of imparting charging to the toner T by frictional charging with the toner T.
  • the agitator 42 is rotated by a rotation driving mechanism, and agitates the toner T and conveys the toner T to the supply roller 43 side.
  • Multiple agitators 42 may be provided with different blade shapes and sizes.
  • the type of toner T is arbitrary, and in addition to powdered toner, polymerized toner using suspension polymerization method or emulsion polymerization method can be used.
  • a toner having a small particle diameter of about 8 to 8 m is preferable, and the shape of the toner particles varies from a nearly spherical shape to a potato-like one with a deviated spherical force. Can be used.
  • the polymerized toner is excellent in charge uniformity and transferability, and is suitably used for high image quality.
  • the transfer device 5 uses a device using any method such as an electrostatic transfer method such as corona transfer, roller transfer, belt transfer, pressure transfer method, adhesive transfer method, etc., which is not particularly limited in type. be able to.
  • the transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like disposed so as to face the electrophotographic photoreceptor 1.
  • the transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charging potential of the toner T, and transfers the toner image formed on the electrophotographic photosensitive member 1 to a transfer material (paper, medium) P. To do. In the present invention, this is effective when the transfer device 5 is placed in contact with the photosensitive member via a transfer material.
  • the cleaning device 6 there are no particular restrictions on the cleaning device 6, and any tally device such as a brush cleaner, magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, etc. can be used.
  • the cleaning device 6 scrapes off residual toner adhering to the photoreceptor 1 with a cleaning member and collects the residual toner. However, if there is little or almost no toner remaining on the surface of the photoreceptor, the cleaning device 6 may be omitted.
  • the fixing device 7 includes an upper fixing member (fixing roller) 71 and a lower fixing member (fixing roller) 72, and a heating device 73 is provided inside the fixing member 71 or 72.
  • FIG. 3 shows an example in which a heating device 73 is provided inside the upper fixing member 71.
  • the upper and lower fixing members 71 and 72 are made of a known heat fixing member such as a fixing roll in which a metal base tube such as stainless steel or aluminum is coated with a silicone rubber, a fixing roll coated with fluorine resin, or a fixing sheet. Can be used. Further, each of the fixing members 71 and 72 may be configured to supply a release agent such as silicone oil in order to improve releasability, or may be configured to force pressure to be mutually forced by a panel or the like. .
  • the fixing device is not particularly limited in its type, and fixing devices of any type such as heat roller fixing, flash fixing, oven fixing, pressure fixing and the like can be provided.
  • an image is recorded as follows. That is, first, the surface (photosensitive surface) force of the photoreceptor 1 is charged by the charging device 2 to a predetermined potential (for example -600V). At this time, charging may be performed by superimposing an AC voltage on a DC voltage that may be charged by a DC voltage. Subsequently, the photosensitive surface of the charged photoreceptor 1 is exposed by the exposure device 3 according to the image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. Then, the developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photoreceptor 1.
  • a predetermined potential for example -600V
  • the developing device 4 thins the toner T supplied by the supply roller 43 with a regulating member (developing blade) 45 and has a predetermined polarity (here, the same potential as the charging potential of the photosensitive member 1). And negatively charged), transported while being carried on the developing roller 44, and brought into contact with the surface of the photoreceptor 1.
  • a toner image corresponding to the electrostatic latent image is formed on the photosensitive surface of the photoreceptor 1.
  • This toner image is transferred onto the recording paper P by the transfer device 5. Thereafter, the toner force remaining on the photosensitive surface of the photosensitive member 1 without being transferred is removed by the cleaning device 6.
  • the image forming apparatus may be configured to perform, for example, a static elimination process.
  • the neutralization process is a process of neutralizing the electrophotographic photosensitive member by exposing the electrophotographic photosensitive member, and a fluorescent lamp, LED, or the like is used as the neutralizing device.
  • the light used in the static elimination process is often light having an exposure energy that is at least three times that of the exposure light.
  • the image forming apparatus may be further modified.
  • the image forming apparatus may be configured to perform a pre-exposure process, an auxiliary charging process, or the like, or may be configured to perform offset printing. Further, a full color tandem system configuration using a plurality of types of toners may be used.
  • Rutile type titanium dioxide with an average primary particle size of 40 nm (“TT055N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL81” manufactured by Toshiba Silicone Co., Ltd.) 17 ”) with a Henschel mixer, 90 parts of a surface-treated titanium oxide, 30 parts of methanol (hereinafter sometimes referred to as“ MeOH ”), tetrahydrofuran (hereinafter referred to as“ THF ”). Koji Kogyo Co., Ltd.
  • Liquid SE2 "was prepared.
  • the cumulative 90% particle size of metal oxide particles in SE2 was 0.12 / zm.
  • Polyvinyl butyral rosin (ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) 15 parts by weight of n-butyl alcohol was mixed and stirred. Furthermore, 15 parts by weight of phenolic resin (SK103, manufactured by Sumitomo Jures Co.) was added and stirred. In addition, add “Titanium Oxide Dispersion TB 1” to this solution, and further filter with a PTFE membrane filter (Advantech Mytex LC) with a pore size of 5 ⁇ m. Coating solution SE4 ” was prepared. The cumulative 90% particle size of metal oxide particles in SE4 was 0.13 m.
  • Tianium Oxide Dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed, and a ball mill is used with an alumina ball (HD manufactured by Nitsuka To Co., Ltd.) having an average particle diameter of about 5 mm.
  • the coating liquid SP1 for forming the undercoat layer was prepared in the same manner as in Example 1 except that the dispersion slurry obtained by dispersing for 5 hours in the above was used as it was (it was not dispersed using an ultra-apex mill). .
  • Tianium oxide dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed, and a ball mill is used with an alumina ball (HD manufactured by Nitsuka To Co., Ltd.) having an average particle diameter of about 1 mm.
  • alumina ball HD manufactured by Nitsuka To Co., Ltd.
  • Tianium Oxide Dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed together, and an alumina ball with a diameter of about 5 mm (manufactured by Nitsukato Co., Ltd.)
  • Titanium Oxide Dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed and dispersed in a ball mill for 5 hours using an alumina ball (HD from Nippon Kato) with a diameter of about 5 mm.
  • “Undercoat layer forming coating solution SP4” was prepared in the same manner as in Example 4 except that the dispersion slurry obtained in this manner was used as it was (without being dispersed using an Ultra Apex mill).
  • Titanium Oxide Dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed and dispersed in a ball mill for 5 hours using an alumina ball (HD from Nippon Kato) with a diameter of about 5 mm.
  • “Undercoat layer forming coating solution SP5” was prepared in the same manner as in Example 5 except that the dispersed slurry obtained in this manner was used as it was (without being dispersed using an ultra-apex mill).
  • Titanium Oxide Dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol and 60 parts of tetrahydrofuran are mixed and dispersed in a ball mill for 5 hours using an alumina ball (HD from Nippon Kato) with a diameter of about 5 mm.
  • a coating solution SP6 for forming an undercoat layer was prepared in the same manner as in Example 6 except that the dispersion slurry obtained in this manner was used as it was (without being dispersed using an ultra-apex mill).
  • Tianium oxide dispersion TB1 90 parts of surface-treated titanium oxide, 30 parts of methanol, and 60 parts of tetrahydrofuran are mixed together, and the ball mill is used with a Zirco Your Ball (HD manufactured by Nitsukato Co., Ltd.) having a diameter of about 0.5 mm.
  • “Undercoat layer forming coating solution SP7” was prepared in the same manner as in Example 1 except that the dispersed slurry obtained by dispersing for 5 hours was used as it was (it was not dispersed using an ultra-avex mill). did.
  • Table 2 summarizes the preparation conditions of the coating solution for forming the undercoat layer in Examples 1 to 6 and Comparative Examples 1 to 7.
  • undercoat layer forming coating solutions SE 1 to SE6 and “undercoat layer forming coating solutions SP1 to SP7” obtained in Examples 1 to 6 and Comparative Examples 1 to 7, the production time and the room temperature were 10 days.
  • Viscosity after storage Rate of change (the difference between the viscosity after storage for 10 days and the viscosity at the time of preparation divided by the viscosity at the time of preparation) and the particle size distribution of the titanium oxide at the time of preparation, and the volume average particle diameter Mv, number average The particle diameter ⁇ was determined.
  • Viscosity was measured using a vertical viscometer (product name ED, manufactured by Tokimec Co., Ltd.) according to a method according to JIS 8803, and the particle size distribution was measured using UPA. The results are also shown in Table 3.
  • Example 1 SE 1 5 0. 0 8 3 2 0. 0 6 3 1 1. 3 1
  • Example 2 SE 2 9 0. 0 9 1 9 0. 0 6 6 3 1. 3 8
  • Example 3 SE 3 1 0 0. 0 8 9 4 0. 0 6 5 2 1. 3 7
  • Example 4 SE 4 2 0. 0 8 5 3 0. 0 7 2 2 1. 1
  • Example 5 SE 5 3 0. 0 7 9 3 0. 0 6 5 4 1. 2 1
  • Example 6 SE 6 3 0. 0 7 3 2 0. 0 6 1 6 1. 1
  • 2 9 1 0. 8 9 0 0 1 .4 5 Comparative Example 2 SP 2 5 1 1 1 .2 5 2 1 0. 8 7 4 1 1 .3 Comparative Example 3 SP 3 3 8 0. 1 3 2 5 0. 0 8 9 6 1.
  • the coating liquid for forming the undercoat layer produced by the method of the present invention has a small average particle diameter and a small particle diameter distribution width, and therefore forms a uniform undercoat layer with high liquid stability.
  • the viscosity change is small and the stability is high even after long-term storage.
  • the uniformity of the undercoat layer formed by coating the undercoat layer forming coating solution is high.
  • Undercoat layer forming coating solution SE1 is applied by dip coating onto an aluminum cutting tube with an outer diameter of 24 mm, a length of 236.5 mm, and a wall thickness of 0.75 mm to a thickness of 2 m after drying. Then, it was heat-cured at 150 ° C. for 2 hours to form an undercoat layer. When the surface of the undercoat layer was observed with a scanning electron microscope, almost no agglomerates were observed.
  • this dispersion 10 parts by weight of polyvinyl butyral (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denkabutyral” # 6000C), 253 parts by weight of 1,2-dimethoxyethane, 85 parts by weight of 4-methoxy-4-
  • a membrane filter made of PTFE with a pore size Mytecs LC made by Advantech
  • a coating solution for charge generation layer was prepared. This charge generation layer coating solution was applied by dip coating and dried to form a charge generation layer on the undercoat layer such that the film thickness after drying was 0.4 m.
  • a charge transport layer coating solution prepared by dissolving 0.05 part by weight of silicone oil in 640 parts by weight of tetrahydrofuran Z toluene (8Z2) mixed solvent was applied so that the film thickness after drying was 17 m. Air-dried at room temperature for 25 minutes. Further, it was dried at 125 ° C. for 20 minutes to provide a charge transport layer to produce an electrophotographic photoreceptor.
  • This electrophotographic photosensitive member is referred to as a photosensitive member E1.
  • a photoconductor E2 was produced in the same manner as in Example 11 except that the undercoat coating solution was changed to SE2 instead of SE1. In this case, when the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, almost no aggregates were observed.
  • a photoconductor E3 was produced in the same manner as in Example 11 except that the undercoat coating solution was changed to SE3 instead of SE1. In this case, when the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, almost no aggregates were observed.
  • the undercoat forming coating solution was the same as in Example 11. Photoconductor E4 was produced. In this case, when the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, almost no aggregates were observed.
  • a photoconductor E5 was produced in the same manner as in Example 11 except that the undercoat coating solution was changed to SE5 instead of SE1. In this case, when the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, almost no aggregates were observed.
  • Photoreceptor E6 was produced in the same manner as in Example 11 except that SE6 was used instead of SE1 as the undercoat-forming coating solution, and it was cured by irradiation with a high-pressure mercury lamp for 1 hour. When the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, almost no agglomerates were observed.
  • a photoconductor E7 was produced in the same manner as in Example 11 except that the film thickness of the undercoat forming coating film was changed to 5 / zm. When the surface of the undercoat layer at this time was observed with a scanning electron microscope in the same manner as in Example 11, almost no aggregates were observed.
  • Photosensitive member P1 was produced in the same manner as in Example 11 except that the undercoat-forming coating solution was SP1 instead of SE1.
  • the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, aggregates were observed.
  • a photoconductor P2 was produced in the same manner as in Example 11 except that the undercoat coating solution was SP2 instead of SE1.
  • the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, aggregates were observed.
  • a photoconductor P3 was produced in the same manner as in Example 11 except that the undercoat-forming coating solution was SP3 instead of SE1.
  • the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, aggregates were observed.
  • a photoconductor P5 was produced in the same manner as in Example 11 except that the undercoat coating solution was SP5 instead of SE1.
  • the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, aggregates were observed.
  • a photoconductor P6 was produced in the same manner as in Example 11 except that the undercoat coating solution was SP6 instead of SE1.
  • the surface of the undercoat layer was observed with a scanning electron microscope in the same manner as in Example 11, aggregates were observed.
  • Example 17 a photoconductor P7 was produced in the same manner as in Example 17 except that the thickness of the undercoat coating film was 5 m.
  • the surface of the undercoat layer at this time was observed with a scanning electron microscope in the same manner as in Example 17, aggregates were observed, and the smoothness and uniformity of the film were not maintained.
  • the dielectric breakdown strengths of the photoreceptors E1 to E7 and the photoreceptors Pl to P7 prepared in Examples 11 to 17 and Comparative Examples 11 to 17 were measured as follows. That is, the photoconductor is fixed in an environment of a temperature of 25 ° C. and a relative humidity of 50%, and a charging roller is pressed against a charging roller having a volume resistivity of about 2 ⁇ ′cm and shorter than the drum length by about 2 cm at both ends. 3 kV was applied and the time until breakdown was measured. The results are summarized in Table 4.
  • the photoconductor is mounted on an electrophotographic characteristic evaluation device (basic and applied electrophotographic technology, edited by Electrophotographic Society, Corona, pages 404 to 405) manufactured according to the Electrophotographic Society measurement standard. Then, after charging the surface potential to 700 V, irradiate a 780 nm laser beam at an intensity of 5.0 / zjZcm 2 and measure the surface potential 100 msec after exposure to a temperature of 25 ° C and relative humidity. The measurement was performed in a 50% environment (hereinafter sometimes referred to as “NN environment”) and in an environment at a temperature of 5 ° C. and a relative humidity of 10% (hereinafter also referred to as “LL environment”). Let them be VL (NN) and VL (LL), respectively. The results are summarized in Table 4. [0241] [Table 4]
  • the electrophotographic photosensitive member of the present invention has a uniform undercoat layer without aggregation or the like, and has a small potential fluctuation due to environmental differences and excellent dielectric breakdown resistance.
  • the undercoat layer forming coating solution of the present invention can be easily manufactured by increasing the thickness of the undercoat.
  • the charge generation layer coating solution prepared in the same manner as in Example 11 was applied by dip coating so that the film thickness after drying was 0.4 m on the undercoat layer, and then dried. A generation layer was formed. Next, an electrophotographic photosensitive member was produced on the charge generation layer in the same manner as in Example 11 except that the following points were changed.
  • a coating solution prepared by dissolving 0.05 part by weight of silicone oil in 640 parts by weight of a mixed solvent of tetrahydrofuran Ztoluene (8Z2) was applied so that the film thickness after drying was 10 m, and dried to obtain a charge.
  • a transport layer was provided to produce an electrophotographic photoreceptor.
  • the photoconductor produced was printed on a Seiko Epson color printer (Product name: InterColor).
  • Rutile-type titanium oxide with an average primary particle size of 40 nm (“TT055N” manufactured by Ishihara Sangyo Co., Ltd.) and 3% by weight of methyldimethoxysilane (“TSL81 17” manufactured by Toshiba Silicone Co., Ltd.) with respect to the titanium oxide.
  • 1 kg of raw slurry made by mixing 50 parts of surface-treated titanium oxide obtained by mixing with a Henschel mixer and 120 parts of methanol, Zirco-Abyz (Nitsukato Co., Ltd.) with a diameter of about 100 ⁇ m YTZ) is used as a dispersion medium, and the ultracapex mill (UAM-015 type) manufactured by Kotobuki Kogyo Co., Ltd. with a mill volume of about 0.15L is used.
  • a mixed solvent of the titanium oxide dispersion and methanol Z1-propanol Z-toluene, and epsilon prolatatam [compound represented by the following formula ( ⁇ )] ⁇ bis (4 amino-3-methylcyclohexyl) Methane [compound represented by the following formula (B)] Z-hexamethylenediamine [compound represented by the following formula (C)] Z decamethylene dicarboxylic acid [compound represented by the following formula (D)] Zoctadeca Polyamide of copolymerized polyamide having a composition molar ratio of methylenedicarboxylic acid [compound represented by the following formula (E)] of 60% Z15% Z5% Z15% Z5% strength is stirred and mixed with heating to mix the polyamide.
  • ultrasonic dispersion is performed for 1 hour using an ultrasonic oscillator with an output of 1200W, followed by filtration with a PTFE membrane filter (Advantech Mytex LC) with a pore size of m, and surface-treated titanium oxide Z Mutual weight
  • the composite polyamide has a weight ratio of 3Z1 and a mixed solvent of methanol Z1-propanolZtoluene with a weight ratio of 7/1/2 and contains a solid content of 18.0% by weight for forming an undercoat layer.
  • a coating solution X was obtained.
  • the charge generation layer coating solution prepared in the same manner as in Example 11 has a thickness of 0 on the undercoat layer after drying. It will be In this way, a charge generation layer was formed by applying and drying by dip coating. Next, a charge transport layer was formed on the charge generation layer in the same manner as in Example 22 to produce an electrophotographic photoreceptor.
  • the produced photoreceptor was mounted on a cartridge of a color printer (product name: InterColor LP-1500C) manufactured by Seiko Epson Corporation. When a full-color image was formed, a good image could be obtained. Obtained image 1. Table 5 shows the number of minute color points observed in a 6 cm square.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 21 except that SP1 was used as the coating solution for forming the undercoat layer.
  • SP1 was used as the coating solution for forming the undercoat layer.
  • Table 5 shows the number of minute color points observed in a 6cm square.
  • An electrophotographic photosensitive member was produced in the same manner as in Example 21 except that SP5 was used as the coating solution for forming the undercoat layer.
  • SP5 was used as the coating solution for forming the undercoat layer.
  • Table 5 shows the number of minute color points observed in a 6 cm square.
  • the electrophotographic photosensitive member of the present invention has very excellent performance with few characteristics of image, such as fogging, color point, and the like, as well as good characteristics of the photosensitive member, resistance to dielectric breakdown. Also for adhesion It was also excellent.
  • Undercoat layer forming coating solution SE6 is applied onto an aluminum cutting tube with an outer diameter of 24 mm, a length of 236.5 mm, and a wall thickness of 0.75 mm so that the film thickness after drying is 2 m.
  • a charge generating material represented by the following formula: 1. 5 parts,
  • a coating solution for forming a charge generation layer having a concentration of 4.0% by weight was prepared. This charge generation layer forming coating solution was dip coated on the undercoat layer so that the film thickness after drying was 0.6 m, and then dried to form a charge generation layer.
  • the electrophotographic photosensitive member obtained above is mounted on an electrophotographic characteristic evaluation apparatus (manufactured by Mitsubishi Chemical Corporation) manufactured in accordance with the standard of the Electrophotographic Society, and charging, exposure, potential measurement, static elimination are performed according to the following procedures. The electrical characteristics were evaluated according to the cycle.
  • the initial surface potential of the photoconductor was measured when the photoconductor was charged by discharging at a grid voltage of 800 V of a scorotron charger in a dark place. Next, irradiate the halogen lamp with 450 nm monochromatic light using an interference filter, measure the irradiation energy jZcm 2 ) when the surface potential is 350 V, and set this value as the sensitivity E1Z2. , initial charge collector position is - 714V, sensitivity E1Z2 is 3. was 23 jZcm 2. The initial charging potential has a higher value of V ⁇ ⁇ (the absolute value of the potential is larger! / ⁇ ), and the sensitivity with better chargeability indicates that the smaller the value is!
  • the undercoat layer-forming coating solution of the present invention can be used for a long time without gelation or precipitation of acid-titanium particles.
  • changes in physical properties such as viscosity are small, Even if the coating is dried on the support and dried to form an undercoat layer, the film thickness is uniform.
  • the electrophotographic photosensitive member having the undercoat layer can form high-quality images even under various usage environments, it can be widely used in the fields of printers, FAX machines, copiers, and the like. It is. It should be noted that the entire contents of the specification, claims, drawings and abstract of the Japanese Patent Application No. 2006-138978, filed on May 18, 2006, are incorporated herein by reference. It is included as an indication.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

L'invention concerne un liquide de revêtement destiné à former une couche sous-jacente présentant une grande stabilité, un photorécepteur électrophotographique haute performance permettant de former des images haute qualité dans divers environnements d'utilisation, avec un niveau réduit de défauts d'images tels que taches noires, taches de couleur et voiles, un dispositif d'imagerie employant le photorécepteur et une cartouche électrophotographique employant le photorécepteur. Le liquide de revêtement pour la formation de couche sous-jacente pour un photorécepteur électrophotographique contient des particules d'oxyde métallique et un liant résine durcissable, et est caractérisé en ce le diamètre particulaire moyen en volume (Mv) des particules d'oxyde métallique dans le liquide de revêtement, mesuré par un procédé de diffusion de lumière dynamique, est inférieur ou égal à 0,1 µm. En variante, le liquide de revêtement pour la formation de couche sous-jacente pour un photorécepteur électrophotographique est caractérisé en ce le diamètre particulaire moyen en volume (Mv) est inférieur ou égal à 0,1 µm, et le rapport entre le diamètre particulaire moyen en volume (Mv) et le diamètre particulaire moyen en nombre (Mp) (Mv/Mp) obéit à la relation suivante 1,10 ≤ Mv/Mp ≤ 1,40 (1).
PCT/JP2007/060272 2006-05-18 2007-05-18 Liquide de revêtement destiné à former une couche sous-jacente dans un photorécepteur électrophotographique et procédé de fabrication de ce liquide Ceased WO2007136012A1 (fr)

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Cited By (1)

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JP2016139052A (ja) * 2015-01-28 2016-08-04 富士ゼロックス株式会社 電子写真感光体、プロセスカートリッジ、画像形成装置

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JP5516574B2 (ja) * 2009-03-31 2014-06-11 大日本印刷株式会社 塩基発生剤、感光性樹脂組成物、当該感光性樹脂組成物からなるパターン形成用材料、当該感光性樹脂組成物を用いたパターン形成方法並びに物品
TWI659593B (zh) * 2018-05-11 2019-05-11 建準電機工業股份有限公司 馬達

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JPH0324558A (ja) * 1989-06-21 1991-02-01 Mitsubishi Kasei Corp 電子写真感光体
JPH07271078A (ja) * 1994-03-25 1995-10-20 Fuji Xerox Co Ltd 下引き層を有する電子写真感光体
WO1996039251A1 (fr) * 1995-06-06 1996-12-12 Kotobuki Eng. & Mfg. Co., Ltd. Broyeur humide d'agitation a billes et procede
JP2005234321A (ja) * 2004-02-20 2005-09-02 Canon Inc 電子写真感光体、プロセスカートリッジおよび電子写真装置
JP2006085172A (ja) * 2004-09-16 2006-03-30 Xerox Corp 光導電性画像形成部材

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0324558A (ja) * 1989-06-21 1991-02-01 Mitsubishi Kasei Corp 電子写真感光体
JPH07271078A (ja) * 1994-03-25 1995-10-20 Fuji Xerox Co Ltd 下引き層を有する電子写真感光体
WO1996039251A1 (fr) * 1995-06-06 1996-12-12 Kotobuki Eng. & Mfg. Co., Ltd. Broyeur humide d'agitation a billes et procede
JP2005234321A (ja) * 2004-02-20 2005-09-02 Canon Inc 電子写真感光体、プロセスカートリッジおよび電子写真装置
JP2006085172A (ja) * 2004-09-16 2006-03-30 Xerox Corp 光導電性画像形成部材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016139052A (ja) * 2015-01-28 2016-08-04 富士ゼロックス株式会社 電子写真感光体、プロセスカートリッジ、画像形成装置

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